### U.S. C HEMICAL 

### S AFETY AND 

### H AZARD 

### I NVES TIGATION 

### B OARD


# HAZARD INVESTIGATION

Report No. 2001

- 01

- H Iss ue Date: October 2002 

# I MPROVING 

# R EACTIVE 

# H AZARD 

# M ANAGEMENT

K EY 

## I SSUES 

## :

• R EGULATORY C OVERAGE

• NFPA H AZARD R ATING S YSTEM

• M ANAGEMENT S YSTEM G UIDANCE

• I NDUSTRY I NITIATIVESReactives Hazard Investigation 10
- 17
- 02


## Contents

EXE CUTIVE SUMMARY

................................ ................................ ................................ ................. 1

1.0 INTRODUCTION

................................ ................................ ................................ ................ 17

1.1 Objectives

................................ ................................ ................................ ............................ 18

1.2 Scope

................................ ................................ ................................ ................................ ... 19

1.3 Investigative Process

................................ ................................ ................................ ............. 19

1.4 Background

................................ ................................ ................................ .......................... 20

1.5 Stakeholder Involveme nt

................................ ................................ ................................ ....... 21

1.6 Public Hearing

................................ ................................ ................................ ...................... 22

2.0 UNDERSTANDING REACTI VE HAZARDS

................................ ................................ ....... 25

2.1 Definition

................................ ................................ ................................ ............................. 25

2.2 Characterization of Reactive Hazards

................................ ................................ ..................... 26

3.0 PROFILE AND CAUSES O F REACTIVE INCIDENTS

................................ ........................ 28
Napp Technologies

................................ ................................ ................................ ............... 28
Bartlo Packaging, Inc.

................................ ................................ ................................ ........... 29

3.1 Data Sources and Methods

................................ ................................ ................................ .... 29

3.2 Data Limitations

................................ ................................ ................................ ................... 30

3.3 Assessment of Reactive Incidents

................................ ................................ .......................... 34Reactives Hazard Investigation 10
- 17
- 02

3.3.1 Injuries and Fata lities

................................ ................................ ................................ 34

3.3.2 Consequences

................................ ................................ ................................ ........... 36
Whitehall Leather Company

................................ ................................ ................................ .. 37

3.3.3 Pro

perty Damage

................................ ................................ ................................ ...... 38
Concept Sciences, Inc.

................................ ................................ ................................ .......... 39

3.3.4 Public Impact

................................ ................................ ................................ ........... 40

3.4 P rofile of Affected Industries

................................ ................................ ................................ . 40

3.5 Profile of Reactive Incidents

................................ ................................ ................................ .. 42

3.5.1 Chemical Classes

................................ ................................ ................................ ...... 42

3.5.2 Type of Reactions

................................ ................................ ................................ ..... 42

3.5.3 Type of Equipment

................................ ................................ ................................ ... 43
BP Amoco Polymers, Inc.

................................ ................................ ................................ ..... 45

3.6 Common Reactive Hazards and Causal Information

................................ ................................ 46

3.6.1 Reactive Hazards

................................ ................................ ................................ ...... 46

3.6.2 Causal In

formation

................................ ................................ ................................ ... 46

4.0 NFPA HAZARD RATING S YSTEM

................................ ................................ .................... 48

5.0 REGULATORY ANALYSIS

................................ ................................ ................................ 53

5.1 OSHA

................................ ................................ ................................ ................................ .. 53Reactives Hazard Investigation 10
- 17
- 02

5.1.1 Overview

................................ ................................ ................................ ................. 53

5.1.2 Process Safety Management

................................ ................................ ...................... 54

5. 1.2.1 Development of PSM Standard

................................ ................................ .... 54

5.1.2.2 Process Safety Information and Process Hazard Analysis

.............................. 55

5.1.3 General Duty Clause

................................ ................................ ................................ . 57

5.1.4 Other PSM Initiatives

................................ ................................ ............................... 57

5.2 EPA

................................ ................................ ................................ ................................ ..... 59

5.2.1 Overview

................................ ................................ ................................ ................. 59

5.2.2 Accidental Release Prevention Requirements (40 CFR 68)

................................ .......... 60

5.2.3 General Duty Clause

................................ ................................ ................................ . 61

6.0 MANAGEMENT SYSTEM GU IDANCE

................................ ................................ .............. 63

6.1 Hazard Identification

................................ ................................ ................................ ............ 64

6.1.1 Existing Sources of Data

................................ ................................ ........................... 65

6.1.2 Chemical Incompatibility

................................ ................................ .......................... 66

6.1.3 Thermal Hazards

................................ ................................ ................................ ...... 67

6.1.4 Chemical Reactivity Testing

................................ ................................ ...................... 68

6.1.5 Accessibility of Chemical Reactivity Test Data

................................ .......................... 69

6.2 Hazard Evaluation

................................ ................................ ................................ ................ 69Reactives Hazard Investigation 10
- 17
- 02

6.2.1 Quantitative Methods

................................ ................................ ................................ 70

6.2.2 Qualitative Methods

................................ ................................ ................................ .. 71

6.3 Management of Change

................................ ................................ ................................ ........ 72

6.4 Personnel Training and Procedures

................................ ................................ ........................ 73

6.5 Summary

................................ ................................ ................................ ............................. 74

7.0 INDUSTRY INITIATIVES

................................ ................................ ................................ ... 76

7.1 Responsible Care Process Safety Code

................................ ................................ ................... 76
7.1.1 Guidance on Implementation

................................ ................................ ...................... 78

7.1 .2 SOCMA Guidance on Implementation

................................ ................................ ......... 79

7.2 NACD Responsible Distribution Process

................................ ................................ ................ 79

8.0 ALTERNATIVES FOR IMP ROVING REGULATORY CO VE RAGE

................................ .... 81

8.1 Improved Coverage Under OSHA PSM

................................ ................................ ................. 81

8.1.1 Highly Reactive Substance Classification

................................ ................................ ... 81

8.1.2 Coverage Based on Hazard Evaluations

................................ ................................ ..... 82

8.1.3 “Safety Case”

................................ ................................ ................................ .......... 83

8.2 Improved Coverage Under EPA RM P

................................ ................................ .................... 84

8.3 Regulatory Relief Absent Catastrophic Consequences

................................ ............................ 84

8.4 Improvements in OSHA PSM and EPA RMP Requirements

................................ ................... 85Reactives Hazard Investigation 10
- 17
- 02

8.4.1 Improved Process Safety Information

................................ ................................ ........ 85

8.4.2 Improved Process Hazard Analysis

................................ ................................ ........... 85

8.4.3 Improved Reporting Requirements

................................ ................................ ............ 86

8.5 Regulatory Initiatives Under Review by New Jersey

................................ .............................. 86

9.0 CONCLUSIONS

................................ ................................ ................................ ................. 87

10.0 RECOMMENDATIONS

................................ ................................ ................................ ..... 89

11.0 REFERENCES

................................ ................................ ................................ .................... 96

APPENDIX A: GLOSSA RY

................................ ................................ ................................ ........... 99

APPENDIX B: SURVEY S

................................ ................................ ................................ ............ 105

B.1 Industry Survey

................................ ................................ ................................ ................. 105

B.2 SOCMA Survey

................................ ................................ ................................ ................ 106

APPENDIX C: SITE V ISITS

................................ ................................ ................................ ........ 107

C.1 Company Profiles

................................ ................................ ................................ .............. 107

C.2 Analysis of Practices for Reactive Chemical Hazard Management

................................ ........ 108

APPENDIX D: RESOUR CES

................................ ................................ ................................ ....... 123

D.1 Guidelines

................................ ................................ ................................ ......................... 123

D.2 Future Guidance

................................ ................................ ................................ ................ 125

D.3 ASTM Codes and Standards

................................ ................................ ............................... 127Reactives Hazard Investigation 10
- 17
- 02

D.4 Select Resources on Reactive Haza rds

................................ ................................ ................ 127

APPENDIX E: HAZARD INVESTIGATION DATA S OURCES

................................ .................... 130

APPENDIX F: STATIS TICAL REVIEW OF OCCU PATIONAL FATALITIES

.............................. 133

APPENDIX G: IDENTI FYING HAZARDS USING CHEMICAL REACTIVITY TESTING

........... 135Reactives Hazard Investigation 10
- 17
- 02


### Figures

1 Case Study: Fire and Explosion, Napp Technologies Inc., April 21, 1995*
2 Case Study: F

ire and Explosion, BPS Inc., May 8, 1997*
3 Total Incidents by Year, 1980

– 2001

................................ ................................ ....................... 34
4 Explosion, Terra Industries, December 13, 1994*
5 Fire and Explosion, Shell Chemical Company, May 27, 1994*
6 Categorization of Consequences of Incidents

................................ ................................ .......... 36
7 Case Study: Chem ical Reaction, Cargo Transfer, Whitehall Leather Company, June 4, 1999*
8 Incidents Resulting in Large Property Losses

................................ ................................ .......... 38
9 Case Study: Explosion, Concept Sciences, Inc., February 19, 1999*
10 Industry Profile, 1980

– 2001

................................ ................................ ................................ .. 41
11 Fire and Explosion, Chief Su pply Corporation, March 26, 1997*
12 Explosion, Georgia Pacific, September 10, 1997*
13 Equipment Involved in Incidents, 1980

– 2001

................................ ................................ ......... 44
14 Case Study: Thermal Decomposition, BP Amoco Polymers, Inc., March 13, 2001*
15 NFPA Instability Rating Analysis, 1980

– 2001

................................ ................................ ........ 48

*These photographs are not available for website posting. They will be placed in the printed copy.Reactives Hazard Investigation 10
- 17
- 02



### Tables
1 Limitations of Common Public Databases

................................ ................................ .......... 32

2 Incidents With Three or More Fatalities

................................ ................................ ............. 35

3 Common Classes of Chemicals Involved in Rea ctive Incidents

................................ ........... 42

4 Analysis of Causal Information

................................ ................................ ......................... 47

5 NFPA

- Defined Degrees of Instability Hazards

................................ ................................ ... 50

6 ACC Responsible Care Safety Management Practices

................................ ........................ 77

D

- 1 Select Resources on Reactive Hazards

................................ ................................ ............. 128

F

- 1 Review of Occupational Fatalities

................................ ................................ ................... 134Reactives Hazard Investigation 10
- 17
- 02



### Acron yms and Abbreviations

ACC American Chemistry Council AFL

- CIO American Federation of Labor

- Congress of Industrial Organizations AIChE American Institute of Chemical Engineers AIHA American Industrial Hygiene Association ANSI American National St andards Institute API American Petroleum Institute APELL Awareness and Preparedness for Emergencies at Local Level (UNEP) ARC Accelerating rate calorimeter (Arthur D. Little, Inc.) ARIP Accidental Release Information Program (EPA) ASSE American S ociety of Safety Engineers ASTM American Society for Testing and Materials BLS U.S. Bureau of Labor Statistics BPS Bartlo Packaging, Inc. °C Degrees Celsius CAAA Clean Air Act Amendments of 1990 CAER Community awareness and emergency response ( ACC Responsible Care) cal/g Calorie per gram CCPS Center for Chemical Process Safety CDCIR The Community Documentation Centre on Industrial Risk (MAHB) CFR Code of Federal Regulations CHETAH Chemical Thermodynamic and Energy Release Evaluation (AS TM) CHRIS Chemical Hazards Response Information System (USCG) CIMAH Control of Industrial Major Accident Hazards (U.K.) CIRC Chemical Incident Reports Center (CSB)Reactives Hazard Investigation 10
- 17
- 02


### Acronyms and Abbreviations (cont’d)

COMAH Control of Major Accident Hazards Involving Dangerous Substances (U.K.,

replaced CIMAH in 1999) CSB U.S. Chemical Safety and Hazard Investigation Board CSI Concept Sciences, Inc. DOE U.S. Department of Energy DSC Differential scanning calorimetry DTA Differential thermal analysis EC Euro pean Community EHS Environmental health and safety EHS Extremely hazardous substance EPA U.S. Environmental Protection Agency EPCRA Emergency Planning and Community Right

- to

- Know Act EU European Union °F Degrees Fahrenheit FMEA Failure modes and effects analysis GDC General Duty Clause (OSHA) HA Hydroxylamine HarsNet Hazard Assessment of Highly Reactive Systems Thematic Network HASTE The European Health and Safety Database HAZOP Hazard and operability HSE Health and Safety Executive (U.K.) HSEES Hazardous Substances Emergency Events Surveillance (MAHB) IAFF International Association of Fire FightersReactives Hazard Investigation 10
- 17
- 02


### Acronyms and Abbreviations (cont’d)

IChemE Institution of Chemical Engineers (U.K.) ICWU International Chemical Workers Union (n ow part of UFCW) IMIS Integrated Management Information System (OSHA) IPD Instantaneous power density ISA Instrumentation, Systems, and Automation Society MAHB Major Accident Hazard Bureau (European Communities) MARS Major Accident Reporting Syst em (MAHB) MHIDAS Major Hazard Incident Data Service (HSE) MOC Management of change MSDS Material safety data sheet MSV Management systems verification NACD National Association of Chemical Distributors NAICS North American Industry Classificatio n System NFIRS National Fire Incident Reporting System NFPA National Fire Protection Association NIST National Institute of Standards and Technology NOAA National Oceanic and Atmospheric Administration NRC National Response Center (USCG) NTSB N ational Transportation Safety Board OCAW Oil, Chemical, and Atomic Workers (now part of PACE) OSHA Occupational Safety and Health Administration PACE Paper, Allied

- Industrial, Chemical & Energy Workers International Union PHA Process hazard analysi s PSCMS Process Safety Code Measurement System (ACC)Reactives Hazard Investigation 10
- 17
- 02 

### Acronyms and Abbreviations (cont’d)
psi Pound per square inch PSI Process safety information PSM Process safety management (OSHA) QA Quality assurance R&D Research and development RDP Respo nsible Distribution Process (NACD) redox Oxidation

- reduction RMP Risk management program (EPA) SIC Standard industrial classification SOCMA Synthetic Organic Chemical Manufacturers Association SOP Standard operating procedure TCDD Dioxin TCP 2 ,4,5

- Tricholorophenol TCPA Toxic Catastrophe Prevention Act (New Jersey) TGA Thermogravimetric analysis TNO Netherlands Organisation for Applied Scientific Research UFCW United Food and Commercial Workers International Union UNEP United Nations E nvironmental Programme UNITE Union of Needletrades, Industrial, and Textile Employees USCG U.S. Coast Guard USWA United Steelworkers of America VSP Vent size packaging W/mL Watt per milliliterReactives Hazard Investigation 10
- 17
- 02, page 1



## Executive Summary

ES.1 Introduction The capability of che mical substances to undergo reactions, or transformations in their structure, is central to the chemical processing industry. Chemical reactions allow for a diversity of manufactured products. However, chemical reactivity can lead to significant hazards if not properly understood and controlled.
Reactivity 1 is not necessarily an intrinsic property of a chemical substance. The hazards associated with reactivity are related to process

- specific factors, such as operating temperatures, pressures, quantitie s handled, concentrations, the presence of other substances, and impurities with catalytic effects.
Safely conducting chemical reactions is a core competency of the chemical manufacturing industry. However, chemical reactions can rapidly release large qu antities of heat, energy, and gaseous byproducts. Uncontrolled reactions have led to serious explosions, fires, and toxic emissions. The impacts may be severe in terms of death and injury to people, damage to physical property, and effects on the environ

ment. In particular, incidents at Napp Technologies in 1995 and Morton International in 1998 raised concerns about reactive hazards to a national level. These and other incidents across the United States 2 underscore the need to improve the management of reactive hazards.

1 See Appendix

A, Glossary, for a definition of “reactivity” and numerous other technical terms. 2 For example: BPS, Inc., West Helena, Arkansas (1997), with three fatalities; Condea Vista, Baltimore, Maryland (1998), with five injured; Whitehall Leather Company, Whit ehall, Michigan (1999), with one fatality; and Concept Sciences, Inc., Allentown, Pennsylvania (1999), with five fatalities and 14 injured.Reactives Hazard Investigation 10
- 17
- 02, page 2

A variety of legal requirements and regulations govern the hazards associated with highly hazardous chemicals (including reactive chemicals), among which are regulations of the Occupational Safety and Health Administration (OSHA) and th e U.S. Environmental Protection Agency (EPA).
OSHA develops and enforces standards to protect employees from workplace hazards. In the aftermath of the reactive incident that caused the Bhopal tragedy, 3 OSHA was concerned about the possibility of a catas trophe at chemical plants in the United States. Its own investigations in the mid

1980s indicated a need to look beyond existing standards.
Bhopal and a series of other major incidents underscored the need for increased attention to process safety manag

ement; OSHA began to develop a standard that would incorporate these principles. A proposed standard was published in 1990. Additionally, the Clean Air Act Amendments (CAAA) of 1990 required OSHA to promulgate a standard to protect employees from the haz ards associated with releases of highly hazardous chemicals, including reactive chemicals.
In 1992, OSHA promulgated its Process Safety Management (PSM) Standard (29 CFR 1910.119). The standard covers processes containing individually listed chemicals t hat present a range of hazards, including reactivity, as well as a class of flammable chemicals. Reactive chemicals were selected from an existing list of chemicals identified and rated by the National Fire Protection Association (NFPA) because of their i nstability rating of “3” or “4” (on a scale of 0 to 4). 4 , 5
CAAA also required EPA to develop regulations to prevent the accidental release of substances, including reactives, that could have serious effects on the public or the environment. In 1996, EPA

3 On December 4, 1984, approximately 40 metric tons of methyl isocyanate was accidentally released in Bhopal India. The incident resulted in an estimated 2,000 deaths within a short period (Lees, 1996; App. 5). 4 OSHA used the 1975 version of NFPA 49, Hazardous Chemicals Data. 5 An NFPA instability rating of “4” means that materials in themselves are readily capable of detonation or explosive decomposition or explosive reaction at normal temperatures and pressures. A rating of “3” means that materials in themselves are capable of detonation or explosive decomposition or explosive reaction, but require a strong initiatin g source or must be heated under confinement before initiation.Reactives Hazard Investigation 10
- 17
- 02, page 3

promulgated its Accidental Release Prevention Requirements: Risk Management Programs (RMP; 40 CFR 68) in response to the congressional mandate. Although this standard established new measures with regard to public notification, emergency response, and accident reporting, its requirements for managing process safety are similar to those of the OSHA PSM Standard. For purposes of this regulation, EPA identified covered substances based on toxicity and flammability

– but not chemical reactivity.

Profession al and trade associations such as the American Institute of Chemical Engineers (AIChE), the American Chemistry Council (ACC), the Synthetic Organic Chemical Manufacturers Association (SOCMA), and the National Association of Chemical Distributors (NACD) pro vide voluntary chemical process safety guidance to their members.
In 1985, AIChE established the Center for Chemical Process Safety (CCPS) in response to the Bhopal tragedy. Manufacturers, government, and scientific research groups sponsor CCPS, which h as published extensive industry guidance in the area of process safety technology and management. CCPS recently produced a safety alert on reactive hazards, and a more comprehensive product is under development.
ACC and SOCMA each have programs to promo te good practices among member companies in the area of chemical process safety. Similarly, NACD promotes good distribution practices and dissemination of information to end

- use customers on the proper handling of chemical products.
This report, Hazard Investigation: Improving Reactive Hazard Management , by the U.S. Chemical Safety and Hazard Investigation Board (CSB), examines chemical process safety in the United States

– specifically, hazardous chemical reactivity. Its objectives are to:

• Determine t

he impacts of reactive chemical incidents.

• Examine how industry, OSHA, and EPA currently address reactive chemical hazards.Reactives Hazard Investigation 10
- 17
- 02, page 4

• Determine the differences, if any, between small, medium, and large companies with regard to reactive chemical policies, practices , in

- house reactivity research, testing, and process engineering.

• Analyze the appropriateness of, and consider alternatives to, industry and OSHA use of the NFPA instability rating system for process safety management.

• Develop recommendations for reducin g the number and severity of reactive chemical incidents.


## ES.2 Investigative Process CSB completed the following tasks:

• Analyzed reactive incidents by collecting and reviewing available data.

• Surveyed current reactive hazard management practices in indu stry.

• Visited companies to observe reactive hazard management practices.

• Analyzed regulatory coverage of reactive hazards.

• Met with stakeholders to discuss the problem and approaches to improve the management of reactive hazards.

• Conducted a public heari ng at which further stakeholder inputs were solicited on key findings and preliminary conclusions from the hazard investigation.
The data analysis included evaluating the number, impact, profile, and causes of reactive incidents. CSB examined more than 40 data sources (e.g., industry and governmental databases and guidance documents; safety/loss prevention texts and journals; and industry association, professional society,Reactives Hazard Investigation 10
- 17
- 02, page 5

insurance, and academic newsletters), focusing on incidents where the primary cause was related to chemical reactivity.
For the purposes of this investigation, an “incident” is defined as a sudden event involving an uncontrolled chemical reaction

– with significant increases in temperature, pressure, and/or gas evolution

– that has caused, or has the potential to cause, serious harm to people, property, or the environment.
Through a survey of select small, medium, and large companies, information was gathered about good practices for reactive hazard management within the chemical industry. CSB also visited chemical industry facilities that have implemented programs for managing reactive hazards.


## ES.3 Key Findings
1. The limited data analyzed by CSB include 167 serious incidents in the United States involving uncontrolled chemical reactivity from January 1980 to June 2001. Forty

- eight of these incidents resulted in a total of 108 fatalities. The data include an average of six injury

related incidents per year, resulting in an average of five fatalities annually.

2. Nearly 50 of the 167 inciden ts affected the public. 6

3. Over 50 percent of the 167 incidents involved chemicals not covered by existing OSHA or EPA process safety regulations. 7

6 “ Public impact” is defined as known injury, offsite evacuation, or shelter

- in

- place. 7 OSHA PSM Standard (29 CFR 1910.119) and EPA Accidental Release Prevention Requirements: Risk Manageme nt Programs (RMP) Under the Clean Air Act, Section 112(r)(7) (40 CFR 68).Reactives Hazard Investigation 10
- 17
- 02, page 6

4. Approximately 60 percent of the 167 incidents involved chemicals that either are not rated by NFPA or have “n o special hazard” (NFPA “0”). 8 Only 10 percent of the 167 incidents involved chemicals with NFPA published ratings of “3” or “4.”

5. For the purpose of the OSHA PSM Standard, NFPA instability ratings have the following limitations with respect to identifying reactive hazards:

• They were originally designed for initial emergency response purposes, not for application to chemical process safety.

• They address inherent instability only, not reactivity with other chemical substances (with the exception of water) or chemical behavior under nonambient conditions.

• NFPA Standard 49 9

– on which the OSHA PSM

- listed highly reactive chemicals are based

– covers only 325 chemical substances, a very small percentage of the chemicals used in industry. 10

• The OSHA PSM Standard lists 137 highly hazardous chemicals

– only 38 of which are considered highly reactive based on NFPA instability ratings of “3” or “4.”

• The NFPA ratings were established by a system that relies, in part, on subjective criteria and judgment.

8 An NFPA instability rating of “0” means that materials in themselves are normally stable, even under “fire” conditions. 9 NFPA 49, Hazardous Chemicals Data (1975 Edition). 10 The Chemical Abstracts Service maintains data on over 200,000 chemicals that are listed under national and international regulations.Reactives Hazard Investigation 10
- 17
- 02, page 7

6. As a result of the j oint OSHA

- EPA chemical accident investigation of the Napp Technologies incident in April 1995, a recommendation was made by EPA and OSHA to consider adding more reactive chemicals to their respective lists of chemicals covered by process safety regulations . To date, neither OSHA nor EPA process safety regulations have been modified to better cover reactive hazards.

7. Reactive hazards are diverse. The reactive incident data analyzed by CSB included:

• Over 40 different chemical classes (i.e., acids, bases, mon omers, oxidizers, etc.), with no single dominating class.

• Several types of hazardous chemical reactivity, with 36 percent attributed to chemical incompatibility, 35 percent to runaway reactions, and 10 percent to impact

- sensitive or thermally sensitive m

aterials.

• A diverse range of chemical process equipment

– including reaction vessels, storage tanks, separation equipment, and transfer equipment. Storage and process equipment (excluding chemical reaction vessels) account for over 65 percent of the equipme nt involved; chemical reaction vessels account for only 25 percent.
Reactive incidents can result in a variety of consequences, including fire and explosions (42 percent of incidents) as well as toxic gas emissions (37 percent).

8. No one comprehensive data source contains the data needed to adequately understand root causes and lessons learned from reactive incidents or other process safety incidents.

9. Incident data collected by OSHA and EPA provide no functional capability to track reactive incidents so

as to analyze incident trends and develop preventive actions at a national level.Reactives Hazard Investigation 10
- 17
- 02, page 8

10. Causes and lessons learned are reported in only 20 percent of the 167 incidents. (Industry associations, government agencies, and academia typically do not collect this inf ormation.) However, more than 60 percent of the incidents for which some causal information was available involved inadequate practices for identifying hazards or conducting process hazard evaluations; nearly 50 percent involved inadequate procedures for storage, handling, or processing of chemicals. 11

11. Over 90 percent of the incidents analyzed by CSB involved reactive hazards that are documented in publicly available literature accessible to the chemical processing and handling industry. 12

12. Although several

computerized tools 13 and literature resources are available to identify reactive hazards, surveyed companies do not generally use them. In some cases, these tools provide an efficient means of identifying reactive hazards without the need for chemical
te sting.

13. Surveyed companies share chemical data of a general nature for most chemicals (e.g., material safety data sheets [MSDS]) and good handling practices for some. However, detailed reactive chemical test data, such as thermal stability data

– which can b e valuable in identifying reactive hazards

– are not typically shared.

14. Approximately 70 percent of the 167 incidents occurred in the chemical manufacturing industry. Thirty percent involved a variety of other industrial sectors that store, handle, or use ch emicals in bulk quantities.

11 The summation of causal factor statistics exceeds 100 percent because each major incident can, and often does, have more th an one cause. 12 See Section 6.1 for a list of selected literature. 13 National Oceanic and Atmospheric Administration’s (NOAA) The Chemical Reactivity Worksheet, American Society for Testing and Materials’ (ASTM) CHETAH, and Bretherick’s Database of Reac tive Chemical Hazards.Reactives Hazard Investigation 10
- 17
- 02, page 9

15. Only limited guidance on the management of reactive hazards throughout the life cycle of a chemical manufacturing process 14 is currently available to industry through professional societies, standards organizations, government a gencies, or trade associations. There are significant gaps in the following:

• Unique aspects of reactive hazards that should be examined during process hazard analysis (PHA), such as the need for reactive chemical test data, and methods to identify and eval uate worst case scenarios involving uncontrolled reactivity.

• Integration of reactive hazard information into process safety information, operating procedures, training, and communication practices.

• Review of the impact on reactive hazards due to proposed changes in chemical processes.

• Concise guidance targeted at companies engaged primarily in the bulk storage, handling, and use of chemicals to prevent inadvertent mixing of incompatible substances.

16. Several voluntary industry initiatives, such as ACC’s Re sponsible Care and NACD’s Responsible Distribution Process (RDP), provide guidance on process safety management for chemical manufacturers and distributors. However, no voluntary industry initiatives list specific codes or requirements for reactive hazard management.

17. The EPA RMP regulation and the European Community’s Seveso II directive both exempt covered processes from some regulatory provisions, if the facility documents the absence of catastrophic damage from process accidents under reasonable worst case conditions. The

14 A recently initiated CCPS project, Managing Reactive Chemical Hazards, may address this gap in industry guidance.Reactives Hazard Investigation 10
- 17
- 02, page 10

State of New Jersey is also considering similar action in its proposed revisions of the Toxic Catastrophe Prevention Act (TCPA) regulations.


## ES.4 Conclusions

1. Reactive incidents are a significant chemical safety problem.

2. The OSHA PSM Standard has significant gaps in coverage of reactive hazards because it is based on a limited list of individual chemicals with inherently reactive properties.

3. NFPA instability ratings are insufficient as the sole basis for determining covera ge of reactive hazards in the OSHA PSM Standard.

4. The EPA Accidental Release Prevention Requirements (40 CFR 68) have significant gaps in coverage of reactive hazards.

5. Using lists of chemicals is an inadequate approach for regulatory coverage of reactive hazards. Improving reactive hazard management requires that both regulators and industry address the hazards from combinations of chemicals and process

- specific conditions rather than focus exclusively on the inherent properties of individual chemicals.

6. R eactive incidents are not unique to the chemical manufacturing industry. They also occur in many other industries where chemicals are stored, handled, or used.

7. Existing sources of incident data are not adequate to identify the number, severity, and causes of reactive incidents or to analyze incident frequency trends.

8. There is no publicly available database for sharing lessons learned from reactive incidents.

9. Neither the OSHA PSM Standard nor the EPA RMP regulation explicitly requires specific hazards, such

as reactive hazards, to be examined when performing a process hazard analysis.Reactives Hazard Investigation 10
- 17
- 02, page 11

Given that reactive incidents are often caused by inadequate recognition and evaluation of reactive hazards, improving reactive hazard management involves defining and requiri ng relevant factors (e.g., rate and quantity of heat and gas generated) to be examined within a process hazard analysis.

10. The OSHA PSM Standard and the EPA RMP regulation do not explicitly require the use of multiple sources when compiling process safety i nformation.

11. Publicly available resources 15 are not always used by industry to assist in identifying reactive hazards.

12. There is no publicly available database to share reactive chemical test information.

13. Current good practice guidelines on how to effectiv ely manage reactive hazards throughout the life cycle 16 of a chemical manufacturing process are neither complete nor sufficiently explicit.

14. Given the impact and diversity of reactive hazards, optimum progress in the prevention of reactive incidents require s both enhanced regulatory and nonregulatory programs.

15 NOAA’s The Chemical Reactivity Worksheet, ASTM’s CHETAH, and Bretherick’s Database of Reactive Chemical Hazards. 16 “Life cycle” refers to all phases of a chemical manufacturing process

– from conceptualization, process research and development (R&D), engineering design, construction, commissioning, commercial operation, and major modification to decommissioning.Reactives Hazard Investigation 10
- 17
- 02, page 12



## ES.5 Recommendations Occupational Safety and Health Administration (OSHA)
1. Amend the Process Safety Management (PSM) Standard, 29 CFR 1910.119, to achieve more comprehensive control of reactive ha zards that could have catastrophic consequences.

• Broaden the application to cover reactive hazards resulting from process

- specific conditions and combinations of chemicals. Additionally, broaden coverage of hazards from self

- reactive chemicals. In expan ding PSM coverage, use objective criteria. Consider criteria such as the North American Industry Classification System (NAICS), a reactive hazard classification system (e.g., based on heat of reaction or toxic gas evolution), incident history, or catastro phic potential.

• In the compilation of process safety information, require that multiple sources of information be sufficiently consulted to understand and control potential reactive hazards. Useful sources include:

- Literature surveys (e.g., Bretherick’s Handbook of Reactive Chemical Hazards , Sax’s Dangerous Properties of Industrial Materials ).

- Information developed from computerized tools (e.g., ASTM’s CHETAH, NOAA’s The Chemical Reactivity Worksheet).

- Chemical reactivity test data produced by employers or obtained from other sources (e.g., differential scanning calorimetry, thermogravimetric analysis, accelerating rate calorimetry).

- Relevant incident reports from the plant, the corporation, industry, and government.

- Chemical Abstracts Service.Reactives Hazard Investigation 10
- 17
- 02, page 13

• Augment t

he process hazard analysis (PHA) element to explicitly require an evaluation of reactive hazards. In revising this element, evaluate the need to consider relevant factors, such as:

- Rate and quantity of heat or gas generated.

- Maximum operating temperature to avoid decomposition.

- Thermal stability of reactants, reaction mixtures, byproducts, waste streams, and products.

- Effect of variables such as charging rates, catalyst addition, and possible contaminants.

- Understanding the consequences of runaway reaction s or toxic gas evolution.

2. Implement a program to define and record information on reactive incidents that OSHA investigates or requires to be investigated under OSHA regulations. Structure the collected information so that it can be used to measure progre ss in the prevention of reactive incidents that give rise to catastrophic releases. 

### U.S. Environmental Protection Agency (EPA)

1. Revise the Accidental Release Prevention Requirements, 40 CFR 68 (RMP), to explicitly cover catastrophic reactive hazards that have the potential to seriously impact the public, including those resulting from self

- reactive chemicals and combinations of chemicals and
process - specific conditions. Take into account the recommendations of this report to OSHA on reactive hazard cover

age. Seek congressional authority if necessary to amend the regulation.Reactives Hazard Investigation 10
- 17
- 02, page 14

2. Modify the accident reporting requirements in RMP*Info to define and record reactive incidents. Consider adding the term “reactive incident” to the four existing “release events” in EPA’s current 5

- year accident reporting requirements (Gas Release, Liquid Spill/Evaporation, Fire, and Explosion). Structure this information collection to allow EPA and its stakeholders to identify and focus resources on industry sectors that experi enced the incidents; chemicals and processes involved; and impact on the public, the workforce, and the environment. 

### National Institute of Standards and Technology (NIST)
Develop and implement a publicly available database for reactive hazard test inform ation. Structure the system to encourage submission of data by individual companies and academic and government institutions that perform chemical testing. 

### Center for Chemical Process Safety (CCPS)

1. Publish comprehensive guidance on model reactive hazar d management systems. At a minimum, ensure that these guidelines cover:

• For companies engaged in chemical manufacturing: reactive hazard management, including hazard identification, hazard evaluation, management of change, inherently safer design, and ad

equate procedures and training.

• For companies engaged primarily in the bulk storage, handling, and use of chemicals: identification and prevention of reactive hazards, including the inadvertent mixing of incompatible substances.

2. Communicate the finding s and recommendations of this report to your membership.Reactives Hazard Investigation 10
- 17
- 02, page 15



### American Chemistry Council (ACC)
1. Expand the Responsible Care Process Safety Code to emphasize the need for managing reactive hazards. Ensure that:

• Member companies are required to have program s to manage reactive hazards that address, at a minimum, hazard identification, hazard evaluation, management of change, inherently safer design, and adequate procedures and training.

• There is a program to communicate to your membership the availability of existing tools, guidance, and initiatives to aid in identifying and evaluating reactive hazards.

2. Develop and implement a program for reporting reactive incidents that includes the sharing of relevant safety knowledge and lessons learned with your membersh ip, the public, and government to improve safety system performance and prevent future incidents.

3. Work with NIST in developing and implementing a publicly available database for reactive hazard test information. Promote submissions of data by your memb ership.

4. Communicate the findings and recommendations of this report to your membership. 

### Synthetic Organic Chemical Manufacturers Association (SOCMA)

1. Expand the Responsible Care Process Safety Code to emphasize the need for managing reactive hazards. Ensure that:

• Member companies are required to have programs to manage reactive hazards that address, at a minimum, hazard identification, hazard evaluation, management of change, inherently safer design, and adequate procedures and training.Reactives Hazard Investigation 10
- 17
- 02, page 16

• There is a pr ogram to communicate to your membership the availability of existing tools, guidance, and initiatives to aid in identifying and evaluating reactive hazards.

2. Develop and implement a program for reporting reactive incidents that includes the sharing of

re levant safety knowledge and lessons learned with your membership, the public, and government to improve safety system performance and prevent future incidents.

3. Work with NIST in developing and implementing a publicly available database for reactive hazard test information. Promote submissions of data by your membership.

4. Communicate the findings and recommendations of this report to your membership. 

### National Association of Chemical Distributors (NACD)

1. Expand the existing Responsible Distribution Proc ess to include reactive hazard management as an area of emphasis. At a minimum, ensure that the revisions address storage and handling, including the hazards of inadvertent mixing of incompatible chemicals.

2. Communicate the findings and recommendations of this report to your membership.


### International Association of Firefighters Paper, Allied - Industrial, Chemical & Energy Workers International Union (PACE) The United Steelworkers of America Union of Needletrades, Industrial, and Textile Employees (UNITE) United Food and Commercial Workers International Union American Society of Safety Engineers (ASSE) American Industrial Hygiene Association (AIHA) Communicate the findings and recommendations of this report to your membership.Reactives Hazard Investigation 10
- 17
- 02, page 17



## 1.0 Introduction
Safely con ducting chemical reactions is a core competency of the chemical industry. 17 However, chemical reactions can become uncontrolled, rapidly releasing large quantities of heat, energy, and gaseous byproducts. As highlighted below, uncontrolled reactions have led to serious explosions, fires, and toxic emissions.
In April 1995, an explosion and fire at Napp Technologies, in Lodi, New Jersey, killed five employees, injured several others, destroyed a majority of the facility, significantly damaged nearby busi nesses, and resulted in the evacuation of 300 residents from their homes and a school (USEPA

OSHA, 1997) . Additionally, firefighting generated chemically contaminated water that ran off into a river. The property damage exceeded $20 million.
Two years later, an explosion and fire at Bartlo Packaging (BPS, Inc.), in West Helena, Arkansas, killed three firefighters and seriously injured another. Hundreds of residents, including patients at a local hospital, were either evacuated or sheltered

- in

- place (US EPA

- OSHA, 1999) . Property damage was extensive. Major roads were closed; and Mississippi River was traffic halted for nearly 12 hours.
An incident on April 8, 1998, at Morton International, Inc., in Paterson, New Jersey, resulted in nine injuries. Res idents in a 10

- by 10

- block area around the plant sheltered

- in

- place for up to 3 hours, and an estimated 10,000 gallons of contaminated water ran off into a nearby river (USCSB, 2000). Six months later, an explosion and fire at Condea Vista, in Baltimore, Maryland, injured five and caused $14 million in damages (USCSB, 2001). In February 1999, an explosion at Concept Sciences, Inc. (CSI), in Allentown, Pennsylvania, killed five persons, including one worker at an adjacent business (USCSB, 2002a). Fourtee n persons, including six firefighters, were injured. The facility

17 S ee Appendix A, Glossary, for definition of technical terms.Reactives Hazard Investigation 10
- 17
- 02, page 18

was completely destroyed, and several other businesses in the vicinity suffered significant property damage. The blast also shattered windows of homes in a nearby residential area. In Ju ne 1999, a toxic release at Whitehall Leather in Whitehall, Michigan, killed one employee (NTSB, 2000).
Each of these incidents involved an uncontrolled chemical reaction. They vividly illustrate the tragic potential of reactive hazards and offer compelli ng reasons to improve reactive hazard management.



## 1.1 Objectives The U.S. Chemical Safety and Hazard Investigation Board (CSB) conducted this investigation of reactive hazard management in the United States to:

• Determine the impacts of reactive chemical inci dents.

• Examine how industry, the Occupational Safety and Health Administration (OSHA), and the U.S. Environmental Protection Agency (EPA) currently address reactive chemical hazards.

• Determine the differences, if any, between small, medium, and large com panies with regard to reactive chemical policies, practices, in

- house reactivity research, testing, and process engineering.

• Analyze the appropriateness of, and consider alternatives to, industry and OSHA use of the National Fire Protection Association (N FPA) instability rating system for process safety management.

• Develop recommendations for reducing the number and severity of reactive chemical incidents.Reactives Hazard Investigation 10
- 17
- 02, page 19

This report, Improving Reactive Hazard Management , supports the CSB goal of increasing awareness of reactive hazards and reducing the occurrence of reactive incidents.



## 1.2 Scope In addressing reactive hazard management in the United States, this investigation focuses on:

• Chemical manufacturing

– from raw material storage through chemical processing to prod uct storage.

• Other industrial activities involving bulk chemicals, such as storage/distribution, waste processing, and petroleum refining.
Industrial activities involving transportation, pipelines, laboratories, minerals extraction, mining, explosives ma nufacturing, pyrotechnic manufacturing, or military uses are not considered.



## 1.3 Investigative Process The chemical industry evaluates the reactivity of a substance in a variety of ways. With input from key stakeholders, CSB developed the following definitio n of a reactive incident (synonymous with “reactive chemical incident”):
A sudden event involving an uncontrolled chemical reaction

– with significant increases in temperature, pressure, or gas evolution

– that has caused, or has the potential to cause, seri

ous harm to people, property, or the environment. 18

18 The use of the term “sudden” is intended to imply that reactive incidents

– though they may be slow to develop because of reactive chemistry effects over an extended time

– have sudden consequences

.Reactives Hazard Investigation 10
- 17
- 02, page 20

Using this definition, CSB analyzed data to attempt to determine the number, impact, profile, and causes of reactive incidents.
Hazards arising from reactive chemicals are covered by a variety of legal r equirements and regulations, including regulations of OSHA and EPA. CSB examined these authorities and regulations to determine how reactive hazards are currently addressed.
Through site visits and a survey of select small, medium, and large companies (Ap pendices B and C)

– and literature reviews of industry guidance documents

– CSB gathered information on the strengths and limitations of reactive hazard management practices within the chemical industry. Industry facilities with programs for managing reactive hazards were selected for site visits.



## 1.4 Background On April 8, 1998, a runaway reaction during the production of Automate Yellow 96 dye initiated a sequence of events that led to an explosion and fire at the Morton International, Inc., plant in Paterson, New Jersey. On the day of the incident, flammable materials were released as the result of an uncontrolled rapid temperature and pressure rise in a 2,000

- gallon kettle in which ortho

nitrochlorobenzene and 2

- ethylhexylamine were being reacted. Nine empl oyees were injured in the explosion and fire, including two seriously. Potentially hazardous materials were released into the community, and the physical plant was extensively damaged.
The CSB Morton investigation showed that inadequate evaluation and c ommunication of reactive hazards was one important factor in the root and contributing causes of the incident (USCSB, 2000). During the course of the investigation, stakeholders raised concerns and requested further investigation into reactive hazards

– par ticularly in light of similar incidents since 1995.Reactives Hazard Investigation 10
- 17
- 02, page 21

Occasionally, in the course of conducting incident investigations, CSB is alerted to significant safety problems that are beyond the scope of any one particular incident investigation. The Morton inves tigation validated stakeholder concerns that reactive hazards merited a more systemic analysis. Therefore, CSB recommended in its report that a hazard investigation be conducted to study issues associated with the management of reactive hazards. A CSB haz ard investigation examines numerous incidents to better understand the nature and causes of a generic safety problem.


## 1.5 Stakeholder Involvement CSB sought input from various stakeholders to gain insight into differing approaches on how to improve reactive hazard management. CSB staff met with industry, regulatory agencies, professional safety organizations, trade associations, trade unions, and public advocacy groups.
The following stakeholders contributed to this investigation:

• American Chemistry Coun cil (ACC).

• Center for Chemical Process Safety (CCPS).

• Environmental Defense.

• U.S. Environmental Protection Agency (EPA).

• International Association of Firefighters.

• National Association of Chemical Distributors (NACD).

• National Fire Protection Association ( NFPA).

• Occupational Safety and Health Administration (OSHA).

• Paper, Allied

- Industrial, Chemical & Energy Workers International Union (PACE).

• Synthetic Organic Chemical Manufacturers Association (SOCMA).Reactives Hazard Investigation 10
- 17
- 02, page 22

• The Chlorine Institute, Inc.

• The United Steelworkers of America.

• Union of Needletrades, Industrial, and Textile Employees (UNITE).

• United Food and Commercial Workers International Union (UFCW).

• Working Group on Community Right

- to

- Know.


## 1.6 Public Hearing A public hearing was held on May 30, 2002, at the Paterso n, New Jersey, City Hall to communicate findings and conclusions from this hazard investigation and to gather input from interested parties prior to making final recommendations and issuing a final report.
The following questions were published in the Fe deral Register and were the main focus of the public hearing:

• Is there a need to improve coverage of potentially catastrophic reactive hazards under the

OSHA Process Safety Management (PSM) Standard? If so, what approaches should be pursued?

- What criteria could be used in the context of process safety regulations to classify chemical mixtures as “highly hazardous” due to chemical reactivity?

- Should there be a minimum regulatory requirement for reactive hazard identification and evaluation that apples to all facilities engaged in chemical manufacturing?



## - What are alternative regulatory approaches?Reactives Hazard Investigation 10
- 17
- 02, page 23

• For processes already covered under the OSHA PSM Standard, do the safety management requirements of the standard adequately address reactive hazards? If not, wha t should be added or changed?

• Does the EPA Risk Management Program (RMP) regulation provide sufficient coverage to protect the public and the environment from the hazards of reactive chemicals? If not, what should be added or changed?

• What nonregulatory a ctions should OSHA and EPA take to reduce the number and severity of reactive chemical incidents?

Additional issues:

• Suggested improvements to industry guidance or initiatives (e.g., Responsible Care [ACC], Responsible Distribution Process [RDP; NACD]) t o reduce the number and severity of reactive chemical incidents.

• Suggested improvements for sharing reactive chemical test data, incident data, and lessons learned.

• Other nonregulatory initiatives that would help prevent reactive incidents.
CSB staff prese nted the investigation findings and preliminary conclusions to the Board. The public hearing agenda also included panels representing industry, labor, the State of New Jersey, and technical experts in the field of chemical process safety. In addition, th e hearing included eyewitness testimony from victims of reactive chemical incidents. Former Senator Frank Lautenberg (D

- NJ) and Senator Jon Corzine (D

- NJ) gave statements of support for the hazard investigation. Representatives from OSHA and EPA declined an invitation to participate.Reactives Hazard Investigation 10
- 17
- 02, page 24

Following the hearing, a 30

- day period was opened to receive written public comments. All information gathered at the hearing and written public comments were carefully considered before the final report was approved by th e Board.Reactives Hazard Investigation 10
- 17
- 02, page 25



## 2.0 Understanding Reactive Hazards
Reactive hazards are briefly defined and characterized below. However, neither Section 2.0 nor this report in its entirety is intended to substitute for any of the more extensive guides and references on this top ic or to eliminate the need for expert analysis in dealing with reactive hazards.



## 2.1 Definition Process safety management of reactive hazards involves the systematic identification, evaluation, and control of hazardous chemical reactivity at all phases of the process life cycle

– from research and development (R&D) to pilot plant, commercial operation, change management, and decommissioning. It encompasses many types of industrial chemical operations

– from storage and handling to chemical manufacturing and wa ste processing.
CCPS (1989) defines a “hazard” as a chemical or physical condition that has the potential to cause harm to human life, property, or the environment. A “reactive hazard” has the potential to lead to a reactive incident (Section 1.3).

Th ere are several types of hazardous chemical reactivity. A reactive hazard may involve:

• Impact

- sensitive or thermally sensitive materials (i.e., self

- reactive chemicals)

– When subjected to heat or impact, these chemicals may rapidly decompose, resulting in a potentially explosive release of energy.

• Runaway reactions (i.e., self

- reactive chemicals or mixtures)

– In an out

- of

- control reaction involving a chemical or chemical mixture, the rate at which heat is generated exceeds the rate at which it is removed th rough cooling media and surroundings.Reactives Hazard Investigation 10
- 17
- 02, page 26

• Chemical incompatibility between two or more substances

– These hazards occur when a chemical is suddenly mixed or comes into contact with another chemical, resulting in a violent reaction.
Among governmental regulations , voluntary guidelines, or trade association codes of practice, there is no standard approach to classifying hazardous chemical reactivity. A variety of methods are used to address self

- reactivity (e.g., decomposition reactions and some polymerization rea ctions) and chemical incompatibility.
For the purposes of this investigation

– rather than adopting any single definition of a “reactive chemical”

– CSB focuses on the broadest range of practices to identify reactive hazards and to manage the risk of reactiv e incidents. A reactive chemical may include any pure substance or mixture that has the capability to create a reactive incident. CSB defines a reactive incident as a sudden event involving an uncontrolled chemical reaction

– with significant increases in temperature, pressure, or gas evolution

– that has caused, or has the potential to cause, serious harm to people, property, or the environment.



## 2.2 Characterization of Reactive Hazards A reactive hazard exists when changes in chemical structure have the potenti al to generate heat, energy, and gaseous byproducts beyond that which can be safely absorbed by the immediate surroundings (Bretherick, 1999). If the rate of energy release is rapid enough and not adequately controlled, the consequences may be severe and include fires, explosions, or toxic emissions.
Numerous types of chemical reactions pose potential hazards. Literature and incident data highlight the hazards of common industrial reactions, such as polymerization, decomposition, acid

- base, oxidation

- re duction (redox), and reactions with water. Polymerization and decomposition can be classified as “self

- reactions” because they often involve just one chemical substance. However, otherReactives Hazard Investigation 10
- 17
- 02, page 27

substances acting unexpectedly

– such as catalysts or contaminants

– are often required to promote even these reactions. “Chemical incompatibility” requires that two or more substances come into contact. A reactive hazard may involve further, more complicated behavior when an intended chemical reaction releases enough heat an d energy to initiate a second unintended reaction, usually a chemical decomposition.
Therefore, chemical reactivity is not necessarily an intrinsic property of a single chemical substance. The severity of reactive hazards is influenced by process

- specif ic factors, such as operating temperatures, pressures, quantities handled, chemical concentrations, impurities with catalytic effects, and compatibility with other chemicals onsite.
Section 6.0 and Appendix D discuss good practices and guidelines for react ive hazard management.Reactives Hazard Investigation 10
- 17
- 02, page 28



## 3.0 Profile and Causes of Reactive Incidents
The purpose of the CSB data search and analysis was to better understand the impact of reactive incidents by evaluating their number, severity, and causes. Five recent reactive incidents

– which illustrate the diversity of reactive hazards

– are highlighted throughout this section. 

### Napp Technologies On April 21, 1995, an explosion and fire at Napp Technologies in Lodi, New Jersey, killed five employees and destroyed the facility (Figure 1). 1 9 The plant was conducting a toll blending operation to produce a commercial gold precipitation agent. The chemicals involved were water reactive (i.e., aluminum powder, a combustible metal in the form of finely divided particles; and sodium hydrosulfite , a combustible solid).
During the process operation, water was introduced into the blender, probably as a result of a mechanical failure. Operators noticed the production of heat and the release of foul

- smelling gas. During an emergency operation to o ffload the blender of its reacting contents, the material ignited and a deflagration occurred. The most likely cause of this incident was the inadvertent introduction of water into water

- reactive materials (USEPA

- OSHA, 1997).
NFPA rates aluminum powder as “1” and sodium hydrosulfite as “2” for reactivity. Therefore, these chemicals are not included on the OSHA PSM list and are not regulated under that standard. The product of the mixture of aluminum powder and sodium hydrosulfite

– a gold precipitation
age nt

– is not rated by NFPA. However, a material safety data sheet (MSDS) on the chemical from the company contracting with Napp to produce the material gave it an NFPA rating of “3.”

19 Photograph not available for website posting; it will appear in the printed copy.Reactives Hazard Investigation 10
- 17
- 02, page 29

The Napp incident raises questions regarding use of the NFPA rating syste m as the sole basis for regulating reactive hazards (see Section 5.1.3). 

### Bartlo Packaging, Inc. This incident occurred on May 8, 1997 (Figure 2). 20 BPS

– a bulk storage and distribution facility in West Helena, Arkansas

– was repackaging an organic pesti cide, AZM50W. As it was being offloaded into a warehouse, employees noticed smoke coming from the building. City emergency response personnel were notified. A team of four West Helena firefighters was attempting to locate the source of the smoke when a n explosion occurred. A collapsing cinderblock wall killed three of the firefighters, and one was injured.
The most likely cause of the incident was the decomposition of bulk sacks of the pesticide, which had been placed too close to a hot compressor disc harge pipe, and the release of flammable vapors (USEPA

- OSHA, 1999). This case history illustrates that severe reactive incidents can occur even at companies engaged in the simple storage and handling of chemicals. The facility was not covered by OSHA PSM , and AZM50W does not have an NFPA rating.


## 3.1 Data Sources and Methods CSB searched over 40 data sources for incidents that met its definition of a reactive incident (Section 2.1). The data search focused on recent incidents (since 1980) where the primary cause was related to chemical reactivity; however, the 1980 cutoff is not intended to diminish the important lessons learned from prior incidents. The search covered both chemical manufacturing (i.e., raw material storage, chemical processing, and produc t storage) and other industrial activities involving bulk chemicals, such as

20 Photograph not available for website posting; it will appear in the printed copy.Reactives Hazard Investigation 10
- 17
- 02, page 30

storage/distribution, waste processing, and petroleum refining. 21 For purposes of this incident search, only reactive incidents that caused serious consequences 22 were examined.
Sources of incident data include a variety of public

- domain databases, technical literature, and news accounts (Appendix E). Sources are categorized in Appendix E as “reviewed only” if incident data did not meet the CSB definition of “reactive chemical incident” (Section 1.3).



## 3.2 Data Limitations Although the statistics provided in Section 3.3 concerning the number and severity of reactive incidents are grave, existing sources of incident data are inadequate to identify the number, severity, frequency , and causes of reactive incidents. The following limitations affected CSB analysis of incident data:

• No single data source provides a comprehensive collection of chemical incidents from which to retrieve or track reactive incident data.

• Incident data collected by OSHA and EPA provide no functional capability to track the occurrence of reactive incidents with serious worker or public impacts; 23 such data are a valuable resource for analyzing incident trends and developing prevention actions at a nation al level.

21 Incidents involving transportation, pipelines, laboratories, minerals extraction , mining, explosives manufacturing, pyrotechnic manufacturing, or military uses are beyond the scope of this investigation, in addition to events involving simple combustion (i.e., rapid reaction of fuel [liquid, vapor, or dust] with oxygen in air). 22 Serious consequences are injuries or fatalities, significant property damage, environmental contamination, and offsite evacuation or shelter

- in

- place. 23 Research indicates that the OSHA Integrated Management Information System (IMIS) identified 70 percent of the reactive incidents in Section 3.3, but none were tracked as “reactive incidents.” Only 25 percent of the reactive incidents that occurred from June 1994 through June 1999 were reported to EPA. These reports are contained in the RMP 5

- year acciden t histories sent to EPA prior to the June 1999 deadline for initial submissions.Reactives Hazard Investigation 10
- 17
- 02, page 31

• No one comprehensive data source contains the data needed to adequately understand root causes and lessons learned from reactive incidents or other process safety incidents. 24 Table 1 lists the limitations of some public databases.

• It is diffic ult to identify causes and lessons learned in existing sources of process safety incident data because industry associations, government agencies, and academia generally do not collect this information.

• Data sources contained incomplete and sometimes ina ccurate incident information

– for example, on numbers of injuries and community impacts. Descriptions of incidents and causal information were sometimes vague and incomplete.

• There are limited Federal or state requirements to report incidents unless they i nvolve specific
consequences. The results of the CSB incident data analysis are acknowledged as representing only a sampling of recent reactive incident data. This limitation precludes CSB from drawing statistical conclusions on incidence rates or inferri

ng trends in the number or severity of incidents. However, despite these limitations, the data can be used to illustrate the profile and causes of reactive incidents.

24 Only one publicly available database is designed to provide such information. The Accident Database from the Institution of Chemical Engineers (IChemE) contains lessons le arned for one

- fourth of the 12,000 incidents in the database.Reactives Hazard Investigation 10
- 17
- 02, page 32

Table 1 Limitations of Common Public Databases
Data Source (a) Description Years Search ed Strengths Limitations

USCG NRC Data on release

notifications of oil and hazardous substance reports to NRC or EPA regional offices 1982

- Present Extensive range of incidents, including those resulting in a chemical release from a reactive incident All states and localities included Knowledge of incident limited at time of notification, leading to possible inaccuracies No requirement to follow up on reports to improve data quality Relies on company compliance to notify (or third party) Notificatio n requirement is driven by release of specified chemical above reportable quantity Not designed to be a lessons - learned database

OSHA IMIS Records of workplace

inspections, including those prompted by accidents where a worker is injured 1984

- Present Inf ormation from OSHA field inspections, a third party More accurate description of impacts on employees and contractors Keyword indexing allows for easy search and retrieval Not comprehensive, limited to incidents selected by OSHA Inspections without abs tracts cannot be keyword searched; causal information unavailable Designed to assist compliance enforcement, not to report on incident causes Limited information from “State

- Plan” states Not designed to be a lessons - learned database

EPA ARIP Responses to

questionnaires sent by EPA from facilities that have had significant releases; purpose is to learn about causes and consequences of hazardous material incidents 1986

- Present Supplements NRC reports for more significant events Additional information on causal factors, consequences, and company safety programs Data are easily analyzed for common causes Includes all states and localities Survey relies on voluntary compliance Not comprehensive; limited to select cases Checklist approach limits value of information to understand root cause Not designed to be a lessons - learned databaseReactives Hazard Investigation 10
- 17
- 02, page 33

EPA RMP*Info Data about chemical

releases resulting in specific impacts covered under RMP regulation (40 CFR 68) 1994

- Present Provides further information about major events involving specific listed chemicals More accurate data on impacts, causal factors, and corrective actions Includes all states and localities Not comprehensive, limited to events resulting in major harm for a select group of chemicals None of s elected chemicals were listed due to reactivity No requirements to include extensive description of incidents, including causes and lessons learned Checklist approach limits respondent’s choices (no indicator for incidents resulting from reactive hazards ) Not designed to be a lessons - learned database

IChemE Accident Database Reports about chemical

incidents around the world from official government sources, the news media, and company reports 1980

- Present Scope is beyond incidents

reported to or inve stigated by regulatory agencies or first responders Contains lessons learned from 3,000 incidents Only one

- fourth of the 12,000 incidents in the database contain lessons

- learned information

HSE MHIDAS Information taken from

public domain sources worldwi de; however, majority of the 7,000 incidents occurred either in UK or US 1985

- Present Scope is beyond incidents

reported to or investigated by regulatory agencies or first responders No extensive description of incidents, including causes and lessons le arned

U.S. Fire Administration NFIRS Response data submitted

by local fire departments 1980

- Present Includes fire and explosion incidents with no/little release, incidents resulting in property damage only, and near

- misses if fire department was called Limited state participation Represents limited information available to fire department at time of response Checklist approach limits respondent choices Not designed to be a lessons - learned database

CSB CIRC Initial reports about

chemical incidents a

round the world from official government sources, news media, and eyewitnesses 1998

- Present Scope is beyond incidents reported to or investigated by regulatory agencies or first responders Includes domestic and international incidents Not comprehensive, only select incidents included Limited time span Frequent reliance on media accounts limits the depth of initial reports Not designed to be a lessons - learned database

(a) ARIP = Accidental Release Information Program; CIRC = Chemical Incident Reports Center; HSE = Health and Safety Executive, United Kingdom; IChemE = Institution of Chemical Engineers; IMIS = Integrated Management Information System; MHIDAS = Major Hazard Incident Data Service; NFIRS = National Fire Incident Reporting System; NRC = Nati onal Response Center; RMP = Risk Management Program.Reactives Hazard Investigation 10
- 17
- 02, page 34



## 3.3 Assessment of Reactive Incidents Reactive incidents can severely affect workers and the public, as well as cause major economic losses and environmental damage. The limited data available to CSB incl udes 167 incidents over nearly 22 years, as summarized in Figure 3.

0 2 4 6 8 10 12 14 16 18 20

80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 YearNo. of Incidents 167 incidents since 1980, an average of 8 incidents per year

Figure 3. Total incidents by year, 1980

– 2001.



### 3.3.1 Injuries and Fatalities Of the 167 reactive incidents, 48 caused a total of 108 fatalities. Since 1980, CSB d ata show an average of six injury

- related incidents per year, resulting in an average of five fatalities per year. Table 2 provides data on 12 incidents with three or more fatalities (see also Figures 4 and 5). 25 Appendix F presents a 5

- year summary of U .S. Bureau of Labor Statistics data on occupational fatalities.

25 Photographs not available for website posting; they will appear in the printed copy.Reactives Hazard Investigation 10
- 17
- 02, page 35

Table 2
Incidents With Three or More Fatalities

Location Date Fatalities ARCO Chemical Channelview, TX (a) 07/05/90 17 Albright and Wilson Charleston, SC 06/17/91 9 IMC Fertilizer/A

ngus Chemical Sterlington, LA 05/01/91 8 NAPP Technologies Lodi, NJ 04/21/95 5 Concept Sciences Hanover Township, PA 02/19/99 5 Terra Industries Port Neal, IA 12/13/94 4 Bastian Plating Auburn, IN 06/28/88 4 Plastifax Gulfport, MS 06/02/82 3 Merck Barceloneta, Puerto Rico 06/12/86 3 Shell Chemical Belpre, OH 05/27/94 3 BPS Inc. West Helena, AR 05/08/97 3 BP Amoco Augusta, GA 03/13/01 3

(a) Although this incident involved combustion, an uncontrolled peroxide decom position reaction created an oxygen - enriched atmosphere in a tank containing flammable liquids. This incident does not meet the “simple combustion” exclusion in the CSB reactive incident definition because it involved combustion in an oxygen

enriched atmo sphere rather than oxygen in air.Reactives Hazard Investigation 10
- 17
- 02, page 36



### 3.3.2 Consequences In addition to causing injuries and fatalities to plant personnel and the public, reactive incidents can also result in environmental harm and equipment damage. These impacts may be due to fires, explosio ns, hazardous liquid spills, toxic gas releases, or any combination of such (Figure 6). Fires and explosions are the most frequent occurrence in CSB data, followed by toxic gas releases.

Fire/explosion: 42% Hazardous liquid spill: 5% Fire/explosion and

toxic release: 16%

Toxic gas release: 37%

Figure 6. Categorization of conseq uences of incidents. 167 total incidentsReactives Hazard Investigation 10
- 17
- 02, page 37



### Whitehall Leather Company On June 4, 1999, the inadvertent mixing of two incompatible chemicals caused a toxic gas release at Whitehall Leather Company in Whitehall, Michigan (Figure 7). 26 One person was killed, and another was injur ed.
A truck driver arrived at the facility to deliver a load of sodium hydrosulfide solution. The delivery took place on the night shift. During prior deliveries on this shift, the shift supervisor had received only “pickle acid.” (The material commonly known onsite as pickle acid was actually ferrous sulfate.) He assumed that the sodium hydrosulfide was pickle acid and directed the truck driver to unload at the facility’s pickle acid tank. Hydrogen sulfide gas was produced when the sodium hydrosulfid e solution was unloaded into the ferrous sulfate tank. The truck driver was exposed to the gas and died; one Whitehall Leather employee was injured (NTSB, 2000).
The Whitehall Leather case demonstrates that reactive hazards other than thermal runaways in
reactors

– such as inadvertent mixing of incompatible materials

– can cause severe reactive incidents. Neither ferrous sulfate nor sodium hydrosulfide is rated by NFPA, and neither compound is an OSHA PSM

- listed chemical.

26 Photograph not available for website posting; it will appear in the printed copy.Reactives Hazard Investigation 10
- 17
- 02, page 38



### 3.3.3 Property Damage
At least a dozen in cidents in the CSB data resulted in property damage alone exceeding $10 million, with three cases in which loss exceeded $100 million (Figure 8). 27 These numbers do not include further financial losses due to business interruption or lost market share.

$120 $105 $100 $80

$32 $25 $20 $20 $20 $16 $15 $14 $12 $12 $10 $10 $0 $20 $40 $60 $80 $100 $120 $140 $160Port Neal, IASterlington,LABelpre, OHSeadrift, TXAlvin, TXPhiladelphia,PAPasadena,TXMartinez, CALodi, NJChicagoHeights, ILTorrance, CABaltimore,MDChannelview,TXSeadrift, TXGreensBayou, TXCharleston,SC

12/94 05/91 05/94 03/91 01/92 03/82 03/00 01/97 04/95 02/81 11/87 10/98 07/90 07/80 07/81 06/91Property Loss ($MM)

Figure 8. Incidents resulting in large property losses.

27 Property loss figu res are quoted for the year in which they were incurred. The numbers in Figure 8 are not scaled to represent constant dollar valuation of loss.Reactives Hazard Investigation 10
- 17
- 02, page 39



### Concept Sciences, Inc. An explosion that occurred during the distillation of a solution of aqueous hydroxylamine (HA) and potassium sulfate killed four CSI employees an d an employee of an adjacent business on February 19, 1999 (Figure 9, 28 USCSB, 2002a). Fourteen people were injured. The CSI facility, in Hanover Township, Pennsylvania, was completely destroyed. Several local buildings in the industrial park were damag ed, and windows were broken in nearby residences.
On the day of the incident, CSI was in the process of producing its first full

- scale batch of 50 wt

percent HA. After the distillation process was shut down, the HA contained in one of the process tanks explosively decomposed. The last recorded concentration of the HA solution in the tank was 86 wt

- percent. HA has been shown to explosively decompose at high concentrations (i.e., 85
wt

- percent; Koseki and Iwata, 2001).
The CSB investigation determined that CSI did not adequately evaluate the hazards of HA during process development. The explosive decomposition hazard of HA was not adequately translated into CSI’s process design, operating procedures, mitigation measures, or precautionary instructions f

or operators. This incident demonstrates the need for effective reactive hazard management throughout the many phases of the process life cycle

– including development, design, construction, and startup. Furthermore, the offsite fatality dramatically illus trates that reactive incidents can affect the public. HA is not a listed chemical under the EPA RMP regulation. It is an OSHA PSM

- listed chemical and has an NFPA rating of “3.”

28 Photograph not available for website posting; it will appear in the printed copy.Reactives Hazard Investigation 10
- 17
- 02, page 40



### 3.3.4 Public Impact Reactive incidents primarily cause onsite impacts, such as wo rker fatalities and injuries

– and severe business impacts, including lost production and property damage. However, a significant number of incidents have led to public impacts, 29 which include public harm (injury or fatality), offsite evacuation, or shelte r - in

- place. Nearly 50 of the 167 incidents in the CSB data affected the public. At least eight of the 12 reactive incidents listed in Table 2 had public impacts. One of these incidents (CSI) resulted in a public fatality.


## 3.4 Profile of Affected Industrie s Analysis of CSB data shows that reactive incidents are not unique to the chemical manufacturing industry (Figure 10). Although about 70 percent of the 167 incidents occurred in the chemical industry, the remaining 30 percent occurred in other indus tries that use bulk quantities of chemicals

– such as waste processing and petroleum refining.
The BPS incident is an example of a severe reactive incident at a nonchemical manufacturing site. The fire and explosion at Chief Supply Corporation also occurre d at a nonchemical manufacturing facility (Figure 11). 30

29 The definition of publi c impact is based on the criteria for reporting offsite incidents in the EPA RMP regulation (40 CFR 68.42a). “Public” includes anyone except employees or contractors at the facility. 30 Photograph not available for website posting; it will appear in the p rinted copy.Reactives Hazard Investigation 10
- 17
- 02, page 41

Chemical manufacturing:

66% Other 34%

Unknown: 1% Bulk storage/handling (not otherwise specified):

27% Petroleum refining: 2% Waste processing: 3% Storage: 1%

Figure 10. Industry profile, 1980

– 2001. 167 total incidentsReactives Hazard Investigation 10
- 17
- 02, page 42



## 3.5 Profile of Reactive Incidents
3.5.1 Chemical Classes The CSB data analysis shows that reactive incidents are not limited to any o ne chemical or to a few classes of chemicals. Table 3 lists common chemical classes involved in the 167 incidents. None of these classes represent a majority of incidents in the CSB data.

Table 3 Common Classes of Chemicals Involved in Reactive Inciden ts

Chemical Class No. of Incidents (a) Acid 38 Oxidizer 20 Monomer 15 Water 14 Base 12 Organic peroxide 12 Hypochlorite 10 Alcohol 8 Hydrocarbon 7 Inorganic/metal 6 Hydrosulfite 6 Other classes 79

(a) Some incidents involved mo re than one class of chemicals.



### 3.5.2 Type of Reactions A range of chemical reactions can cause reactive incidents. Over 90 percent of the 167 incidents analyzed by CSB involved reactive hazards that are documented in literature available to the chemical proce ssing industry (see Section 7.1). The various types of reactions indicate the diversity of chemistry involved; forReactives Hazard Investigation 10
- 17
- 02, page 43

example, an explosion at a Georgia Pacific resin factory

– involving formaldehyde, phenol, and sulfuric acid

– was caused by an exothermic runaw ay reaction (Figure 12). 31 . Nearly 75 percent of the incidents from the CSB data were caused by one of the following types of reactions:

• Decomposition (26 percent)

• Acid/base (11 percent)

• Water reactive (10 percent)

• Polymerization (10 percent)

• Oxidatio n (6 percent)

• Decomposition initiated by another reaction (5 percent)

• Oxidation

- reduction (4 percent)

• Chlorination, catalytic cracking, halogenation, hydrolysis, and nitration (each 1 percent).
Information was insufficient to determine type of re action for the remaining 23 percent of incidents.



### 3.5.3 Type of Equipment A reactive incident can occur in most equipment used to store, handle, manufacture, and transport chemicals. The CSB data show that incidents occur in a variety of chemical processing a nd storage equipment

– including reactors, storage tanks, and bulk storage drums (Figure 13). Twenty

- five percent of the incidents involved reactor vessels; 22 percent, storage equipment (e.g., tanks, rail cars, and designated storage areas); 22 percent, ot her process equipment (e.g., holding tanks, mixers, and dryers); 13 percent,

31 Photograph not available for website posting; it will appear in the printed copy.Reactives Hazard Investigation 10
- 17
- 02, page 44

waste, separation, and transfer equipment; and 10 percent, bulk storage drums. No particular equipment accounted for 8 percent of the data.

These data contradict a common a ssumption that a majority of reactive incidents involve chemical reactor vessels. Chemical processing and storage equipment (excluding reactors) and bulk storage drums account for over 65 percent of the equipment involved in reactive incidents. The case histories highlighted throughout Section 3.0 are examples of reactive incidents that did not occur in reaction vessels.

Transfer equipment: 5% Reactor: 25%

Storage equipment: 22% Other process equipment: 22% Separation equipment:

5% Unknown: 8%

Stroage drum: 10% Waste equipment: 3%

Figure 13. Equipment involved in incidents, 1980

– 2001. 167 total incidentsReactives Hazard Investigation 10
- 17
- 02, page 45



### BP Amoco Polymers, Inc. On March 13, 2001, t

hree people were killed as the result of a vessel failure and fire at the BP Amoco Polymers plant in Augusta, Georgia (Figure 14, 32 USCSB, 2002b). The facility produces plastics. Startup operations in a process to produce Amodel

– a nylon

- family polymer

– we re suspended due to problems with equipment in a finishing line. During the aborted startup attempt, polymer was discarded into the polymer catch tank, a waste collection vessel. Cooling effects created a layer of hardened plastic 3 to 5 inches thick alo ng the entire inner wall of the vessel, blocking all normal and emergency vents. However, the material in the core of the vessel remained hot and molten. It continued to react and decompose, generating gas that could not escape. Over several hours, the catch tank became pressurized. The failure occurred as workers attempted to open a cover on the vessel.
The CSB investigation determined that BP Amoco was unaware of the hazardous reaction chemistry of the polymer because of inadequate hazard identifica tion during process development. This lack of awareness is a commonly cited cause of reactive incidents within the CSB data. The BP Amoco incident also involved an endothermic (or heat consuming) reaction rather than the more commonly recognized exotherm ic (or heat producing) runaway chemical reaction.

32 Photograph not available for website posting; it will appear in the printed copy.Reactives Hazard Investigation 10
- 17
- 02, page 46



## 3.6 Common Reactive Hazards and Causal Information Identifying common types of associated hazards and causes is an essential element of understanding the reactive incident problem.



### 3.6.1 Reactive Hazards
A c ommon perception is that reactive incidents are primarily the result of runaway reactions. In fact, analysis of data from the 167 incidents suggests that other types of reactive hazards should also be of concern. CSB data analysis identified three common types of reactive hazards (see Appendix A for definitions):

• Chemical incompatibility

• Runaway reaction

• Impact or thermally sensitive materials.
Of the 167 incidents, 36 percent are attributed to chemical incompatibility, 35 percent to runaway reactions, and 10 percent to impact or thermally sensitive materials. The hazard is unknown for 19 percent of the incidents.



### 3.6.2 Causal Information
Causal

33 data are reported for only 37 of the 167 incidents. Analysis of this limited set of data revealed a variety o f causes (Table 4). More than 60 percent of reactive incidents for which some causal information was available involved inadequate management systems for identifying or evaluating hazards. In the CSI

33 The term “cause” within this section refers to inadequate process sa fety management practices. The causal information presented is not intended to be considered as root causes; no consistent root cause analysis methods were identified within the data.Reactives Hazard Investigation 10
- 17
- 02, page 47

incident, even though the reactive hazard was known, an inadequate hazard evaluation was performed. Nearly 50 percent of the causal data also point to inadequate procedures for the safe storage, handling, or processing of chemicals (e.g., Whitehall Leather and BPS).

Table 4 Analysis of Causal Information
Causes Frequency of Attribution
No. of Incidents Incidents With Causal

Information (%) (a) (b) Inadequate hazard identification 9 24 Inadequate hazard evaluation 16 43 Inadequate procedures for storage/handling of reactive chemicals 17 46 Inadequate training for storage/handling of reactive chemicals 10 27 Inadequate management of change (MOC) system to Identify/evaluate reactivity hazards 6 16 Inadequate process design for reactive hazards 6 16 Inadequate design to prevent human error 9 24 Inade quate company

- wide communication of hazards 5 14 Inadequate emergency relief system design 3 8 Inadequate safe operating limits 3 8 Inadequate near miss/incident investigation 2 5 Inadequate inspection/maintenance/monitoring of safety critical devices in reactive chemical service 2 5
Previously unknown reactive hazards 1 3

(a) Causal data are reported for 37 of the 167 incidents. (b) Total greater than 100 percent because each incident may have more than one cause.Reactives Hazard Investigation 10
- 17
- 02, page 48



## 4.0 NFPA Hazard Rating System

CSB an alyzed incident data in terms of the chemicals published in NFPA Standards 49 and 325. The data show that only about 10 percent of the 167 known incidents involved chemicals that were rated NFPA “3” or “4” (Figure 15). NFPA “not rated” or “0” accounts fo r nearly 60 percent of the data.. (Both the BPS and the Morton incidents involved chemicals that were not rated by NFPA.)

Not published in NFPA 49 or 325: 36% NFPA 1: 11% NFPA 4: 3% NFPA 3:

8%

NFPA 2:

20%

NFPA 0: 21%

Figure 15. NFPA instability rating analysis ( formerly reactivity rating ) of incident data, 1980

– 2001.Reactives Hazard Investigation 10
- 17
- 02, page 49

The OSHA PSM Standard lists 137 highly hazardous chemicals

– only 38 of which are considered highly reactive based on NFPA ratings “3” or “4” 34 (as defined in NFPA 704, Standard System for the Identification of the Hazards of Materials for Emergency Respons e).

Public and labor union concerns as the result of a number of reactive incidents have caused OSHA to consider PSM revisions. One alternative OSHA identified through a petition from unions (Section 5.1.3) is to add the remaining NFPA “3” and “4” chemic als and all NFPA “1” and “2” chemicals to the PSM list. However, this approach would address less than half of the chemicals involved in the 167 incidents examined by CSB.
NFPA developed Standard 704 as a tool for identification and evaluation of potentia l hazards during emergency response, not for application to chemical process safety. The instability rating is a part of this standard. It was not intended to be used to measure reactivity, but rather to measure the “inherent” instability of a pure subst ance or product under conditions expected for product storage. The instability rating does not measure the tendency of a substance or compound to react with other substances or any other process

- specific factors, such as operating temperature, pressure, q uantity handled, chemical concentration, impurities with catalytic effects, and compatibility with other chemicals onsite.
NFPA 704 is a voluntary standard. Table 5 lists the five degrees of hazard defined in NFPA 704. The NFPA hazard rating system pri marily relies on qualitative criteria and judgment to assign chemical

34 The PSM chemical list is based on ratings in NFPA 49 (1975). Six o f the 137 PSM chemicals are listed twice. An NFPA instability rating of “4” means that materials in themselves are readily capable of detonation or explosive decomposition or explosive reaction at normal temperatures and pressures (13 of 131 PSM

- listed ch emicals have an NFPA “4” reactivity). A rating of “3” means that materials in themselves are capable of detonation or explosive decomposition or explosive reaction, but require a strong initiating source or must be heated under confinement before initiati

on (25 of 131 PSM

- listed chemicals have an NFPA “3” reactivity).Reactives Hazard Investigation 10
- 17
- 02, page 50

instability ratings, which may vary considerably from company

- to

- company. The instability rating system was so named in 1996 to clarify its intent; it was formerly known as the reactiv ity rating system. NFPA 49 lists the ratings for 325 chemicals

– representing only a very small percentage of the chemicals used in industry. 35

Table 5

NFPA - Defined Degrees of Instability Hazards

NFPA Instability No. Stability Criteria Typically Includes W ater Reactivity Criteria (a) Instantaneous

Power Density Criteria (b)
4 Materials that in themselves are readily capable of detonation or explosive decomposition or explosive reaction at normal temperatures and pressures Materials that are sensitive to l ocalized thermal or mechanical shock at normal temperatures and pressures Not applicable Greater than 1,000 W/mL

3 Materials that in themselves are capable of detonation or explosive decomposition or explosive reaction, but require a strong initiating sou rce or must be heated under confinement before

initiation Materials that are

sensitive to thermal or mechanical shock

at elevated temperatures and pressures Materials that react

explosively with water without heat or confinement; heat of mixing greater tha n

600 cal/g Less than

1,000 but greater than 100 W/mL

2 Materials that readily

undergo violent chemical change at elevated temperatures and pressures Materials that

exhibit an exotherm at temperatures less than 200 o C and materials that polymerize vigorous ly and evolve heat Materials that react

violently with water or form potentially explosive mixtures with water; heat of mixing less than 600 but greater than 100

cal/g Less than 100

but greater than 10 W/mL

35 The Chemical Abstracts Service maintains data on over 200,000 chemicals that are listed under national and international regulations.Reactives Hazard Investigation 10
- 17
- 02, page 51

1 Materials that in

themselves are normally stab le, but can become unstable at elevated temperatures and pressures Materials that

exhibit an exotherm at temperatures greater than 200

o C but less than 500 o C Materials that react

vigorously with water, but not violently; heat of mixing less than 100 but gr

eater than 30 cal/g Less than 10

but greater than 0.01 W/mL

0 Materials that in

themselves are normally stable, even under fire conditions Materials that exhibit an exotherm at temperatures greater than 500

o C when tested by differential scanning calorimet ry (DSC) Materials that do not

react with water; heat of mixing less than 30

cal/g Less than 0.01

W/mL

Source: NFPA 704. (a) cal/g = calories per gram. (b) W/mL = watts per milliliter.

The more recent editions of NFPA 704 provide some objective criter ia (Table 5) for assignment of ratings. The degree of instability hazard is ranked based on “ease, rate, and quantity of energy release” of the substance (NFPA, 1996). Onset temperature, instantaneous power density (IPD; Hofelich et al., 1997), 36 and

– in the case of water

- reactive substances

– the energy of reaction upon mixing are the parameters considered. Onset temperature was added in the 1990 edition of the standard, and the latter two criteria were added in 1996. These criteria are not intended to re place the primarily qualitative nature of the rating system, but to be used as a hazard recognition aid. Where data are available, NFPA currently prefers ratings based on IPD.

36 IPD is calculated as the mathematical product of th e energy of decomposition/reaction and the initial rate of reaction, determined at 482 degrees Fahrenheit (°F; 250 degrees Celsius [°C]).Reactives Hazard Investigation 10
- 17
- 02, page 52

NFPA 49 is no longer issued in the NFPA Fire Code set, and the standard is no longer updated; 37 however, Standard 704 was updated in 2001. NFPA 49 information is available in the Fire Protection Guide to Hazardous Materials (NFPA, 1997).
NFPA confirmed the intent of NFPA 704 and the instability rating system through corresponde nce with CSB staff. The committee clarified that the rating system is insufficient for use as the sole basis of determining reactivity for regulatory lists because it considers only one facet of chemical reactivity. NFPA staff reiterated this position in testimony given at the CSB public hearing on reactive chemical safety on May 30, 2002.

37 Revision of NFPA 49 was withdrawn as a committee project in 1998.Reactives Hazard Investigation 10
- 17
- 02, page 53



## 5.0 Regulatory Analysis

5.1 OSHA
5.1.1 Overview CSB found significant gaps in OSHA process safety regulations designed to protect workers from highly hazardous chemicals, includi ng reactive hazards. OSHA standards cover the hazards of some classes of substances, such as flammable and combustible liquids; however, no OSHA standard specifically addresses reactive hazards.
There are OSHA standards designed to protect employees fro m acute chemical hazards resulting from reactive incidents

– including fires, explosions, and toxic releases. The Hazard Communication Standard (29 CFR 1910.1200) requires chemical manufacturers to evaluate chemicals produced or handled in their workplace a nd to communicate the hazards associated with the products they produce via labels and MSDSs. The standard also requires all employers to provide information to employees about the hazardous chemicals to which they could be exposed. The PSM Standard (29 CFR 1910.119) requires employers to prevent or minimize the consequences of catastrophic releases of highly hazardous chemicals, including highly reactive chemicals.
Numerous other OSHA regulations apply to the chemical industry in general, but are not s pecific to reactive hazards. Where no specific OSHA standards apply, the OSHA General Duty Clause (GDC; Section 5(a)(1) of the 1970 Occupational Safety and Health Act) creates a legal obligation for an employer to address a known hazard, including a react ive hazard.Reactives Hazard Investigation 10
- 17
- 02, page 54



### 5.1.2 Process Safety Management The CSB incident data were analyzed to determine whether the chemicals involved were considered “highly hazardous” under the OSHA PSM Standard. For the purposes of analyzing the data, CSB determined if a chemical wa s covered by OSHA PSM by identifying whether it was listed in PSM or was covered as a flammable chemical by OSHA definition. 38
All 167 incidents were included in the analysis, even if the incident predated the promulgation of PSM:

• In 30 percent of the incidents, the chemicals were covered under PSM.

• In 50 percent of the incidents, the chemicals were not PSM covered.

• In 20 percent of the incidents, it could not be determined whether PSM

- covered chemicals were involved.

CSB was unable to determine from the incident data if a process was PSM covered. 39



### 5.1.2.1 Development of PSM Standard Following a series of very serious chemical accidents in the 1980s, OSHA began to develop the PSM Standard. The proposed standard was published in 1990, the same year that Co ngress enacted the Clean Air Act Amendments (CAAA). Section 304 of CAAA required OSHA to promulgate a chemical process safety standard to protect employees from hazards associated with accidental releases of highly hazardous chemicals in the workplace. I t further required that OSHA develop and apply the standard to a list of

38 Processes that are covered by the OSHA PSM Sta ndard due to the presence of flammable substances may, in fact, have significant reactive hazards as well. An example is a polymerization reaction involving the flammable chemical 1,3

- butadiene. Such processes are required to address all chemical hazard s, including reactive hazards. 39 The CSB analysis is limited by incomplete knowledge of chemical concentrations, quantities, or other covered chemicals in the same process

– all of which are relevant in determining whether a process is regulated under the P SM Standard.Reactives Hazard Investigation 10
- 17
- 02, page 55

highly hazardous chemicals. Congress specified that highly hazardous chemicals included “toxic, flammable, highly reactive, and explosive substances.”

OSHA relied on several establis hed lists

– including the New Jersey Toxic Catastrophe Prevention Act (TCPA), the Delaware Extremely Hazardous Substances Risk Management Act, the European Communities Seveso Directive (82/501/EEC), and NFPA Hazardous Chemicals Data (NFPA 49)

– to develop its list of highly hazardous chemicals. OSHA chose to list the chemicals classified as reactive category “3” or “4” in NFPA 49 (1975 edition).
The OSHA PSM Standard lists 131 distinct chemicals with toxic or reactive properties. 40 It includes 25 chemicals wi

th an NFPA rating of “3” and 13 chemicals with an NFPA rating of “4.” PSM applies to processes that involve listed chemicals at or above threshold quantities and to processes with flammable liquids or gases onsite in one location, in quantities of 10,000 pounds or more. Companies that manufacture explosives and pyrotechnics are also required to comply with the standard.
The OSHA list has not been updated since the promulgation of PSM in 1992. It does not reflect changes in the list of chemicals and the ir ratings made by NFPA in 1991 and 1994.



### 5.1.2.2 Process Safety Information and Process Hazard Analysis The PSM Standard is a performance

- oriented standard that requires the employer to prevent catastrophic releases from covered processes by executing a 14

- eleme nt safety program. All processes with highly hazardous chemicals are required to have a management system that addresses each element of the standard.
As supported by the CSB incident data, two elements are particularly relevant to reactive hazards

– Proc ess Safety Information (PSI; 29 CFR 1910.119 [d]) and Process Hazard Analysis (PHA; 29 CFR 1910.119

40 Six of the 137 chemicals on the PSM list are not distinct (i.e., are listed under a synonym).Reactives Hazard Investigation 10
- 17
- 02, page 56

[e]). Two commonly cited causes of reactive incidents, as shown by the data, are inadequate understanding of reactive chemistry or inadequate hazard evalua tion (Section 3.0; Table 4).
The PSM Standard requires that the following information be contained within the PSI element

– physical data, reactivity data, corrosivity data, thermal and chemical stability data, and hazardous effects of potential inadverten

t mixing of different materials. The standard does not specifically define what is to be included in any of these data categories, the level of detail required, or the method of compilation. 41 It does, however, stipulate that an MSDS can be used to compi le the data to the extent that it contains the information required. In 1996, OSHA issued a Hazard Information Bulletin cautioning that MSDSs do not always contain information about hazards from mixing or blending chemicals (OSHA, 1996).
Another require ment of the PSM Standard is that the employer conduct process hazard analysis, which OSHA defines as “an organized and systematic effort to identify and analyze the significance of potential hazards associated with the processing or handling of highly haza rdous chemicals.” The analysis must identify the hazards of the process and necessary safeguards; however, the standard does not explicitly define requirements for addressing reactive hazards. It is evident that the PSM Standard has significant gaps in co verage of reactive hazards because it is based on a limited list of individual chemicals with inherently reactive properties.

41 Incident data in Section 3.0 illustrate that reactive hazards are broader than the “hazardous effects of potential inadvertent mixing of dif ferent materials.”Reactives Hazard Investigation 10
- 17
- 02, page 57



### 5.1.3 General Duty Clause The OSHA GDC states, “Each employer shall furnish to each of his [sic] employees employment and a place of em

ployment which are free from recognized hazards that are causing or are likely to cause death or serious physical harm to his [sic] employees.” In the event that there is no OSHA standard to address a hazard, OSHA may use the GDC to enforce a legally bind ing requirement on an employer or impose a fine. To substantiate a GDC violation, several criteria must be met, 42 including:

• A condition or activity in the employer’s workplace presents a hazard to employees.

• The cited employee or the employer’s indust ry recognizes the hazard.

• The hazard is likely to cause death or serious physical harm.

• There is a feasible means of eliminating or materially reducing the hazard.
To support a GDC citation, OSHA must establish employer or industry recognition of a hazar d. Among other forms of evidence, industry recognition may be demonstrated by a consensus standard (NFPA, American National Standards Institute [ANSI], American Petroleum Institute [API], American Society for Testing and Materials [ASTM], etc.). Industry standards may also be used to identify feasible means of reducing the hazard. However, no industry consensus standard has been identified for the management of reactive hazards in support of a GDC citation. 43



### 5.1.4 Other PSM Initiatives As a result of the join t OSHA

- EPA chemical accident investigation of the Napp Technologies incident in April 1995, a recommendation was made by both agencies to consider adding more reactive chemicals to

42 OSHA response to CSB interrogatory for the reactive chemical hazard investigation, June 6, 2001. 43 OSHA response to CSB interrogatory for the reactive chemical hazard investigation, June 6, 2001.Reactives Hazard Investigation 10
- 17
- 02, page 58

their respective lists of chemicals covered by process safety regulations. To date, however, neither OSHA nor EPA has modified process safety regulations to better cover reactive hazards.
Following the Napp incident, six labor unions 44 petitioned OSHA for emergency revision of the PSM Standard, stating that it failed to cover re active chemicals. In a followup letter, the labor unions asked OSHA to consider the following issues in any revision of the standard:

• Addition of NFPA category “1” and “2” reactives to the list of highly hazardous chemicals.

• Hazard evaluation, including t he conditions for use of highly hazardous chemicals.

• Adequacy of the NFPA ratings process.

• Synchronization of the OSHA PSM and the EPA RMP lists; and expansion of worker/union involvement.
In February 1996, the Chemical Manufacturers Association (now AC C) and API submitted a letter to OSHA responding to issues raised by the labor unions. The letter indicated ACC support of PSM as an effective standard. It also reflected the opinion that expanding PSM in the ways proposed would greatly increase complian

ce costs without substantial benefits and that a large amount of the additional cost would fall on small businesses. ACC and API identified several alternatives for regulating reactives, but concluded that each presented technical difficulties, significa nt cost, and minimal benefit. For these reasons, both trade groups opposed any revisions to the PSM Standard.

44 Union of Needletrades, Industrial, and Textile Employees (UNITE); United Steelworkers of America (USWA); Oil, Chemical, and Atomic Workers (OCAW); American Federation of Labor

- Congress of Industrial Organizations (AFL

- CIO); International Association of Fire Fighters (IAFF); and Internation al Chemical Workers Union (ICWU). In 1999, OCAW merged with the United Paperworkers International Union to form the Paper, Allied

- Industrial, Chemical & Energy Workers International Union (PACE). In 1996, ICWU merged with the United Food and Commercial W orkers International Union (UFCW).Reactives Hazard Investigation 10
- 17
- 02, page 59

OSHA did not undertake an emergency revision of the PSM Standard in response to the labor unions’ petition. In October 1997, OSHA and EPA issu ed a joint chemical accident investigation report on the Napp Technologies incident. Among the recommendations was that OSHA and EPA review the lists of substances subject to the PSM Standard and RMP regulation (40 CFR 68) to determine whether reactive

su bstances should be added.
The OSHA regulatory agenda published on May 14, 2001, indicated that it intended to reconsider the reactives issue that year. However, in the regulatory agenda published on December 3, 2001, OSHA withdrew from consideration chang es to the PSM Standard. A May 21, 2002, letter from John Henshaw, Assistant Secretary of Labor for OSHA, to CSB stated that issues related to reactives

– though dropped from the current regulatory agenda

– would be reconsidered and possibly raised in future r egulatory agendas.


## 5.2 EPA
5.2.1 Overview Similar to OSHA, EPA has no regulations specifically targeted to reactive hazard management. However, some legal requirements cover limited aspects of reactivity. The EPA RMP and GDC are two such requirements, as discuss ed in more detail below. EPA has made no decision on how to address reactivity because it has not yet identified a technically sound method for determining reactive substances. 45
CSB incident data were analyzed with respect to coverage under the EPA RMP r egulation:

• In 20 percent of the incidents, the chemicals were covered under RMP.

45 EPA response to CSB interrogatory for the reactive chemical hazard investigation, May 31, 2001.Reactives Hazard Investigation 10
- 17
- 02, page 60

• In 60 percent of the incidents, the chemicals were not RMP listed.

• In 20 percent of the incidents, it could not be determined whether RMP

- listed chemicals were involved.

The 1990 CAAA required EPA to promulgate regulations to prevent the accidental release of substances that could cause death, injury, or serious adverse effects to human health or the environment. Congress directed EPA to regulate at least 100 substances and t o take into account several factors when developing a chemical list, including “toxicity, reactivity, volatility, dispersibility, combustibility, or flammability of the substance, and amount of the substance.”



### 5.2.2 Accidental Release Prevention Requirements (40 CFR 68) EPA promulgated the Accidental Release Prevention Requirements (40 CFR 68), which contain the list of regulated chemicals and requirements for facilities possessing more than a threshold quantity of a listed chemical in an individual process. Cov ered facilities are required to implement a risk management program and submit a risk management plan to EPA.
When developing the list of substances, EPA considered only the inherent characteristics of a chemical that indicate a severe threat due to expo sure. Well

- defined criteria were used for toxicity and flammability. However, because of the complexities of site

- specific factors and process conditions, EPA was unable to determine any inherent characteristic as an indicator of reactivity. EPA conclud ed that there was “insufficient technical information for developing criteria for identifying reactive substances.” 46 Consequently, the January 1994 RMP list of 130 chemicals does not contain any substances listed due to reactive hazards.

46 EPA Response to CSB interrogatory for the reactive chemical hazard investigation, May 31, 2001.Reactives Hazard Investigation 10
- 17
- 02, page 61

Unlike OSHA’s use of criteria for covering classes of chemicals, such as the criterion for flammable substances as a class, EPA has used only chemical lists for the RMP regulation. The authority provided by Congress in the CAAA for EPA to develop the Accidental Release Prevention Requirements is explicit on the use of a “List of Substances” (Section 112[r][3]) to identify the covered chemicals.

The list of RMP

- regulated chemicals has not been revised since the October 1997 recommendation by the OSHA

- EPA joint chemical accident investigation team to review the lists of substances subject to the PSM Standard and RMP regulation to determine whether reactive chemicals should be added.
RMP requires covered processes to have a hazard assessment, a prevention program, and an e mergency response program. The hazard assessment must evaluate the accidental release of regulated substances, including the worst case scenario. RMP contains requirements for prevention of accidental releases, which include the same basic elements as th e OSHA PSM Standard. Therefore, the limitations described in Section 5.1.2.2 with respect to process safety information and process hazard analysis also apply to RMP. It is evident that the EPA RMP has significant gaps in coverage of reactive hazards.



### 5.2 .3 General Duty Clause The EPA GDC is a statutory requirement found in Section 112(r)(1) of the 1990 CAAA. It reads as follows:
The owners and operators of stationary sources producing, processing, handling or storing [a chemical in 40 CFR 68 or any other EHS] have a general duty [in the same manner and to the same extent as the OSHA GDC] to identify hazards which may result from such releases using appropriate hazard assessment techniques, to design and maintain a safe facility taking such steps

as are ne cessary to prevent releases, and to minimize the consequences of accidental releasesReactives Hazard Investigation 10
- 17
- 02, page 62

which do occur.
GDC applies to all stationary sources (fixed facilities) that handle, produce, process, or store regulated substances or extremely hazardous substances (EH S) 47 . It obligates facilities to identify and safely manage all hazards, including reactive hazards. Similar to OSHA, EPA can use its GDC enforcement authority to create legally binding requirements or enforce actions for hazards that have not been prope rly identified or managed.
The EPA GDC is not limited solely to hazards addressed by industry standards; however, there are no standards for management of reactive hazards that can be used to enforce a general duty on industry.

The EPA GDC enforcement au thority can be used in either a proactive (before an incident) or a reactive (after an incident) manner. EPA can use its order authority (CAA Section 112[r][9]) to enforce GDC in a case where it finds the possibility of imminent and substantial endangerme nt. EPA has used GDC order authority in only one situation for reactive hazards.

47 The Senate Report on the 1990 CAAA stated that EHS includes substances specifically listed under EPA’s Accidental Release Prevention Requirements (40 CFR 68) and substances listed under Section 302 of the Emergency Planning and Community Right

- to

- Know Act (EPCRA). The defini tion also includes substances not necessarily listed that

–

due to their toxicity, reactivity, flammability, volatility, or corrosivity

– may cause death, injury, or property damage as a result of short

- term exposure upon release to the air.Reactives Hazard Investigation 10
- 17
- 02, page 63



## 6.0 Management System Guidance
Inadequate process safety management practices are often cited as the cause of reactive incidents, as discussed in Section 3.0 (Table 4). Inci dent data underscore the critical importance of successfully implementing the following key elements throughout the life cycle 48 of a manufacturing process:

• Hazard identification

– structured approach to identifying and understanding the reactive hazards of

chemicals used alone or in combination.

• Hazard evaluation

– system for investigating reactive hazards, assessing the potential consequences of uncontrolled reactions, and establishing a safe design and operating basis.

• Management of change (MOC)

– procedure to re

- evaluate reactive hazards when changes occur throughout the life cycle of a chemical process.

• Personnel training and procedures

– program that includes written operating procedures and consideration of the potential for human error in reactive syste ms. CSB staff found a considerable amount of technical guidance for chemists and process engineers on how to identify reactive hazards during the R&D and design phases. This guidance covers chemical manufacturing processes and storage/handling situations.

48 “ Life cycle” refers to all phases of a chemical manufacturing process

– from conceptualization, process R&D, engineering design, construction, commissioning, commercial operation, and major modification to decommissioning.Reactives Hazard Investigation 10
- 17
- 02, page 64

However, only limited guidance is available on the following aspects of reactive hazards management:

• Use of reactive test data, including data from the reactive hazard evaluation.

• Use of a protocol to identify reactive hazards (e.g., checklist or specifi c guidewords).

• Application of a chemical interaction matrix.

• Identification and evaluation of worst case scenarios involving uncontrolled reactivity.

• Integration of reactive hazard information into process safety information, operating procedures, training , and communication practices.

• Evaluation of reactive hazards during MOC procedures.
Companies engaged primarily in the bulk storage, handling, and use of chemicals are particularly in need of concise guidance on preventing the inadvertent mixing of inco mpatible substances.
Additionally, as discussed earlier, though several computerized tools and literature resources are available to identify reactive hazards, the surveyed companies generally do not use them. Also, they typically do not share detailed r eactive chemical test data.



## 6.1 Hazard Identification Understanding and identifying reactive hazards is a key component of process knowledge. It is often the first activity in managing reactive hazards and may occur early in product research or in process d evelopment. Ineffective hazard identification is commonly cited as a cause of reactive incidents. WhereReactives Hazard Investigation 10
- 17
- 02, page 65

some causal information is available from CSB’s data search, 49 about 25 percent of incidents are attributed to this factor.

The identification of re active hazards is a prerequisite to conducting a hazard evaluation and developing safe design, operation, and maintenance practices (CCPS, 1992; pp. 9, 12). A variety of reactive hazard identification methods are currently used, including literature searc hes and screening tests (CCPS, 1995a, 1995b; HSE, 2000; Barton and Rogers, 1997). No one technique is appropriate for all circumstances.



### 6.1.1 Existing Sources of Data Relevant sources of information for reactive hazard data include the following, as noted thr oughout this report and listed in Section 11.0:

• Bretherick’s Handbook of Reactive Chemical Hazards

.

• U.S. Coast Guard (USCG) Chemical Hazard Response Information System (CHRIS) Database.

• NFPA 49, Hazardous Chemicals Data.

• NFPA Fire Protection Guide to Ha zardous Materials

.

• Sax’s Dangerous Properties of Industrial Materials

.

• National Oceanic and Atmospheric Administration (NOAA) The Chemical Reactivity Worksheet.

49 Causal information is available in approxima tely 20 percent of the incidents identified by CSB.Reactives Hazard Investigation 10
- 17
- 02, page 66

• Rapid Guide to Chemical Incompatibilities

.

• ASTM Chemical Thermodynamic and Energy Release Pro gram (CHETAH).
Responses to the CSB industry survey 50 indicate that most companies consult a variety of information sources as a first step in compiling data on reactive hazards. However, respondents prefer literature sources and expert opinion over compu terized tools such as CHETAH, The Chemical Reactivity Worksheet, or Bretherick’s Database of Reactive Chemical Hazards. Such programs can be used to predict the thermal stability of compounds, reaction mixtures, or potential chemical incompatibilities. I n some cases, they provide an efficient means of identifying reactive hazards without having to conduct chemical testing. Survey responses showed that five of nine companies consider computer

- based tools “not valuable.” Only two of the surveyed companies use The Chemical Reactivity Worksheet. 51
CSB data show that hazard information was available in existing literature for over 90 percent of the reactive incidents.



### 6.1.2 Chemical Incompatibility Approximately 36 percent of incidents in the CSB data are relat ed to chemical incompatibility. CCPS provides information on managing chemical incompatibility hazards in guidelines for chemical reactivity. It emphasizes the need to systematically examine possible chemical incompatibilities and describes the use of in teraction matrices (CCPS, 1995a, p. 7; 1995b, p. 108). 52, , 53 This guidance applies to chemical manufacturers as well as to other industries.

50 Appendix B describes the CSB industry survey. 51 The survey did not seek to determine whether the participants had used the tools and concluded that they were of little value, or whether they had onl y a limited understanding of the potential benefits. 52 An interaction matrix indicates whether the combination of two or more materials yields an undesired consequence (see ASTM E2012

- 99, Standard Guide for Preparation of Binary Chemical Compatibility Cha rt). 53 Section 6.1.1 lists data sources for developing an interaction matrix.Reactives Hazard Investigation 10
- 17
- 02, page 67

In many cases, it is not possible to identify hazards through intrinsic chemical properties because they
may be caused by the interaction of process chemicals, either inadvertent or intentional. Such hazards are commonly encountered at facilities primarily engaged in the bulk storage, handling, and use of chemicals. There is limited guidance on segregation and isolation of incompatible substances, handling water

- or air

reactive chemicals, training, and MOC.
Seven of nine respondents use chemical interaction matrices to identify potential chemical incompatibilities. Most use a binary matrix (i.e., the mixing o f only two chemical components at a time). Respondents indicated that literature or expert opinion are important sources of data for the matrix.
Five of the seven respondents who use a matrix also use chemical testing results as a data source. A simila r number review the matrix during qualitative hazard evaluation studies (i.e., hazard and operability [HAZOP] studies, “what

- if,” checklist, etc.).
CCPS (1995a; pp. 46

- 49) provides only limited discussion on when to conduct an incompatibility study or h ow to apply the results during a hazard evaluation. It suggests that the PHA team review the interaction matrix, but does not provide detailed guidance on this subject (CCPS, 1995b; p. 111).



### 6.1.3 Thermal Hazards From the data collected by CSB, 35 percent of the 167 incidents are attributed to runaway reaction hazards. CCPS (1995a, Ch. 2; 1995b, Ch. 3), HSE (2000; pp. 15

- 28), and IChemE (Barton and Rogers, 1997; pp. 20

- 45) offer guidance on methods for identifying thermal hazards such as runaway reactions. I n Guidelines for Safe Storage and Handling of Reactive Materials , CCPS (1995b; p. 58) outlines a materials assessment strategy for hazard identification that applies various recognition aids along with expert judgment and experience. The guidelines sugges t evaluation of each substance stored or handled onsite.Reactives Hazard Investigation 10
- 17
- 02, page 68



### 6.1.4 Chemical Reactivity Testing When there are gaps in literature or expert knowledge of reactive hazards, industry good practice guidelines (e.g., CCPS, 1995a; p. 13) recommend chemical testing prio r to scaleup of a chemical manufacturing process. Chemical reactivity testing can be used either to aid in hazard identification during product research or to evaluate hazards during capital projects. Most survey participants view chemical testing as a v

aluable part of the hazard identification process. Appendix G presents more detailed information on testing.
The survey participants were asked about their reactivity testing programs. Three of five companies visited by CSB use expert opinion to examin e the need for testing. Seven of nine use a mix of in

- house and contracted testing capabilities. Two respondents rely on literature surveys and expert opinion instead of chemical testing. Only two of 10 respondents to a recent SOCMA survey 54 use reactiv e chemical test data to identify hazards. (SOCMA membership includes many small

- and medium

- sized companies.)
Guidance on when to conduct testing is not consistent. When designing processes for conducting chemical reactions, CCPS (1995a; p. 13) suggest s that all materials be subject to screening tests, even if no reactivity concerns are identified in the literature search and expert judgment. In other guidance, CCPS (1995b; p. 85) states that in designing storage and handling systems for reactive mater ials, prior experience, theoretical evaluations, and expert opinion may be used to determine the need for screening
tests.

54 SOCMA conducted a survey of reactive hazard management practices among its 300 member companies during the April 2001 Responsible Care conference. The survey consisted of a two

- page questionnaire distributed at a working session on reactive chemical safety. Ten companies responded. A copy of the survey report was provided to CSB.Reactives Hazard Investigation 10
- 17
- 02, page 69



### 6.1.5 Accessibility of Chemical Reactivity Test Data Although no dedicated data repository for reactive chemical test results is generall y available to industry or the public, a substantial amount of test data have been generated by the chemical industry. One company visited by CSB had compiled a database of over 60,000 reactive chemical test results. Survey participants were asked if suc h data are shared with other companies. CSB investigators determined that the surveyed companies share data of a general nature for most chemicals (i.e., data typically found on an MSDS) and good handling practices for some. This typically does not incl

ude reactive chemical test data. Several reasons were given for the absence of substantial data sharing, including:

• Potential liability concerns

• Need for expert interpretation of reactivity data

• Reluctance to share trade secrets or confidential business information.
Currently, there is no mechanism to effectively share reactive chemical test data throughout industry. The feasibility of a publicly available test database has not yet been studied by industry or government. Reactive chemical experts at one company visited by CSB expressed an interest in working with the National Institute of Standards and Technology (NIST) to develop such a database.


## 6.2 Hazard Evaluation More than 40 percent of the 167 incidents from the CSB data search, where some causal inf ormation is available,

55 are attributed to inadequate hazard evaluation. In several cases, the hazard was known, but its

55 Causal information is available in approximately 20 percent of the incidents identified by C SB.Reactives Hazard Investigation 10
- 17
- 02, page 70

potential magnitude was not

– nor was the potential severity of the consequence. In other cases, the hazard evaluation did not properly identify initiating events.
IChemE acknowledges that “there is no standard procedure for evaluating chemical reaction hazards” (Barton and Rogers, 1997; p. 120). The CSB survey further highlights the variety of approaches to reactive hazard evaluation; companies rely to varying degrees on quantitative and qualitative evaluation methods.



### 6.2.1 Quantitative Methods A prerequisite to any process hazard evaluation is adequate knowledge of the chemistry. Prior to specifying safe design and operating requirements , identified hazards must be evaluated to understand what can go wrong and the potential consequences. CCPS (1995a, p. 17; 1995b, p. 94) and IChemE (Barton and Rogers, 1997; p. 28) provide guidance on parameters for reactive hazard evaluation. Quantitati ve modeling techniques and calorimetry data are sometimes required along with extensive
process - specific information. 56
Both HSE (2000; p. 34) and IChemE (Barton and Rogers, 1997; p. 107) emphasize the need to identify a worst case scenario involving unc ontrolled reaction to ensure that safety systems are designed and maintained to provide adequate protection under all postulated circumstances. When identifying the worst case, IChemE provides a general recommendation to evaluate any scenario not protecte d by high

56 Good practice guidelines illustrate how these parameters are typically examined for both normal and postulated abnormal conditions, such as variations in reactant quantity, concentration, agitation, sequence, time, failure of utilities, and instrume ntation. Qualitative hazard evaluation protocols are not well suited for such complex chemical phenomena (e.g., the severity of an uncontrolled reaction under a loss of electrical power may not be apparent without sufficient test data).Reactives Hazard Investigation 10
- 17
- 02, page 71

integrity shutdown systems. 57 However, there is little guidance on how to systematically identify and evaluate a worst case scenario involving uncontrolled reaction.



### 6.2.2 Qualitative Methods Chemical reactivity information is gathered from data sear ches, calculations, and reactivity testing. Qualitative hazard evaluation is one commonly used approach to assessing process hazards, including reactive hazards (CCPS, 1992).
Several qualitative approaches can be used to identify hazardous reaction scen arios, including process hazard analysis, checklists, chemical interaction matrices, and an experience

- based review. CCPS (1995a; p. 176) describes nine hazard evaluation procedures that can be used to identify hazardous reaction scenarios

– checklists, Dow fire and explosion indices, preliminary hazard analysis, “what

- if” analysis, failure modes and effects analysis (FMEA), HAZOP study, fault tree analysis, human error analysis, and quantitative risk analysis.
Although each of these methods can be useful in identifying reactive scenarios, none are designed specifically to address the reactive hazard. Existing good practice guidelines from CCPS (1992), HSE (2000), and IChemE (Barton and Rogers, 1997) do not adequately address how to manage the unique
aspec ts of reactive hazards while performing hazard evaluations.
The CSB survey identified examples of modified or hybrid techniques to identify reactive hazard scenarios and ensure the implementation of adequate safeguards. For example, companies conducting

r eactions in batch chemical reactors often conduct HAZOP studies by evaluating deviations from

57 Instrumentation , Systems, and Automation Society (ISA) Standard 84, Application of Safety Instrumented Systems for the Process Industries, outlines the principles of high integrity shutdown systems.Reactives Hazard Investigation 10
- 17
- 02, page 72

procedural steps as opposed to deviations from intended equipment design. One company uses a “what

if” PHA protocol specifically designed to address reactivity hazards.
Most survey respondents indicated that they perform reactive hazard evaluation studies during specific life

- cycle phases of a process or product. These phases include process development, commercial process design, periodic re

- evaluation, an d before proposed modifications. The protocol for hazard evaluation of reactive systems varies from company

- to

- company. At a minimum, all surveyed companies employ qualitative hazard evaluations. 58
Industry guidance from CCPS (1995a; 1995b), HSE (2000) , and IChemE (Barton and Rogers, 1997) contains little information on how and when to apply reactive chemical test data during a process hazard analysis. During site visits, CSB investigators encountered PHA teams that use test data to evaluate reactive h azards. In combination with input on reactive chemistry, the test data are used to assist in evaluating appropriate safe operating limits and potential consequences of an uncontrolled reaction.
This practice supports the CSB observation that effective p rocess hazard analysis for a reactive system is essentially more “data driven” than conventional process hazard analysis given the technical complexity of the reactive hazard. Three of the five visited companies use reactivity test data when conducting
pr ocess hazard analysis; two use qualitative hazard evaluation methods only.



## 6.3 Management of Change MOC is a systematic procedure for reviewing potential hazards of proposed changes to facilities. It applies to all hazardous materials regardless of reactivity ; however, there are specific considerations for

58 Qualitative hazard evaluation is commonly referred to as “process ha zards analysis,” or PHA, which is used in OSHA PSM.Reactives Hazard Investigation 10
- 17
- 02, page 73

reactive hazards. Inadequate MOC procedures are a contributing cause of several reactive incidents described in Section 3.0.
For reactive processes, MOC applies to increases or decreases in process temp erature, changes in raw material specifications, concentration changes, process time changes, and changes in materials of construction (HSE, 2000; p. 41). CCPS (1995a, p. 6; 1995b, p. 197) explains that chemical testing may be required to identify and eva luate new hazards from process changes.
Overall, there is a lack of specific guidance on how to evaluate reactive hazards during the MOC procedure. Existing guidelines from CCPS (1995a; 1995b), IChemE (Barton and Rogers, 1997), and HSE (2000) do not addre ss how to maintain and update reactive hazard evaluation as part of the change approval procedure

– nor do they address what type of change to process chemistry or product formulation necessitates a review and possible update of the reactive hazard evaluatio n.


## 6.4 Personnel Training and Procedures Personnel training and performance

– as a management systems element

– focuses on development of process knowledge and documentation, including clearly defined technical information and operating procedures (CCPS, 1989).
Incident data in Section 3.0 show that more than half of the reactive incidents, where some causal information is available, are attributed to inadequate operating procedures and training. These data illustrate the challenge of effectively communicating a practical, working knowledge of an often complex array of chemical and process information.
Personnel who work with reactive chemicals must understand the hazards they face and take precautions to ensure safety (HSE, 2000; p. 42). Training is required fo r both technical personnel (e.g., processReactives Hazard Investigation 10
- 17
- 02, page 74

engineers, chemists) and operators and maintenance personnel. In the Morton case, plant personnel did not have a proper understanding of reactive hazards and were unaware of the potential for a runaway reaction. The Morton case and others described in Section 3.0 show that reactive hazard management requires a working knowledge of the complex intersection of chemical properties and process

- specific conditions.
Both IChemE (Barton and Rogers, 1997; p. 137) and HS E (2000; p. 42) briefly address operator training in systems that involve reactive hazards. None of the guidelines, however, address the transfer and communication of this information to technical personnel. There is little guidance on integrating reacti ve hazard information into operating procedures, training, and communication practices.
At one company visited by CSB, newly appointed production managers are required to demonstrate their knowledge of reactive hazards before a review committee. The basis for technical and managerial training is an established “operating discipline,” an up

- to

- date reference of process knowledge containing technical details, operational details, and process hazard information. This approach to ensuring technical and manage ment personnel training is unique among survey participants.


## 6.5 Summary Guidance on safety management throughout the life cycle of a process is limited. CCPS (1989; 1994) provides a framework for a systems

- based approach to managing chemical process safet y. No organization provides comprehensive guidance on technical and management practices for reactive hazards that applies to all phases of the process life cycle, though CCPS (1995b; pp. 193

- 202) briefly describes how these management principles apply to reactive hazards.
Good management practices include not only hazard identification and evaluation early in R&D, but also issues such as MOC throughout the life of the chemical manufacturing process. The existing body ofReactives Hazard Investigation 10
- 17
- 02, page 75

knowledge is largely focused on technical topics, such as calorimetry testing, engineering design, scaleup, and emergency venting. CCPS currently has a project underway that addresses technical and management practices for reactive hazards.Reactives Hazard Investigation 10
- 17
- 02, page 76



## 7.0 Industry Initiatives
Voluntary industry i

nitiatives supplement regulatory requirements. The chemical industry has voluntarily undertaken several initiatives to provide guidance on chemical process safety, including processes involving reactive hazards. However, at present, no industry initiativ es list specific codes or requirements for reactive hazard management.



## 7.1 Responsible Care Process Safety Code Approximately 70 percent of incidents in CSB data occurred in the chemical manufacturing industry. Both ACC and SOCMA have programs to promote good practices among their member companies in the area of chemical process safety. 59 In 1989, ACC developed the Responsible Care Process Safety Code 60 to prevent fires, explosions, and accidental chemical releases. The code and its accompanying resour ce guidelines include a series of recommended management practices.
Responsible Care is intended to apply throughout the life cycle of a process

– from conception and design through construction and startup, and continuing with long

- term operation of the facility. The safety practices are divided into four areas, as listed in Table 6. Although many practices are similar to requirements of the OSHA PSM Standard, the Responsible Care Process Safety Code includes such additional elements as accountability, multiple safeguards, and performance measurement. The ACC and SOCMA bylaws obligate member companies to participate in Responsible Care, which includes making good faith efforts to implement the program elements. Companies are required to undergo a self

evaluation process; a third

- party management systems verification (MSV) audit is optional.

59 Currently, ACC has approximately 190 member and partner companies, representing 1,700 facilities. SOCMA

– with 300 member companies, representing 2,000 facilities

– has been a Responsible Care Partner Ass ociation since 1990. 60 Approximately 30 chemical industry associations are Responsible Care Partner Associations.Reactives Hazard Investigation 10
- 17
- 02, page 77

Table 6 ACC Responsible Care Safety Management Practices
Management Leadership in Process Safety 1

– Commitment 2

– Accountability 3

– Performance Measurem ent 4

– Incident Investigation 5

– Information Sharing 6

– Community Awareness and Emergency Response (CAER) Integration Process Safety Management of Technology 7

– Design Documentation 8

– Process Hazards Information 9

– Process Hazard Analys is 10

– Management of Change Process Safety Management of Facilities 11

– Siting 12

– Codes and Standards 13

– Safety Reviews 14

– Maintenance and Inspection 15

– Multiple Safeguards 16

– Emergency Management Managing Personnel for Process Safety 17

– Job Skills 18

– Safe Work Practices 19

– Initial Training 20

– Employee Proficiency 21

– Fitness for Duty 22

– ContractorsReactives Hazard Investigation 10
- 17
- 02, page 78



### 7.1.1 Guidance on Implementation ACC has published a resource guide to aid member companies in implementing the Responsible C are Process Safety Code (ACC, 1989). Although the guide provides suggestions on how to continually improve process safety, it does not prescribe how to comply with the code. It does not list specific requirements for reactive hazard management, but does require management systems to be developed

– several of which could apply to reactive hazards as determined by each member company.
Currently, ACC highlights reactive hazard management only in the following areas:

• Management Practice 7, Design Documentatio n, which emphasizes the need to develop and retain process description, chemistry, and “reaction data.”

• Management Practice 8, Process Hazards Information, which describes the need to maintain current, accessible information on material characteristics, in cluding “reactivity.”
Management Practice 12, Codes and Standards, discusses the need to identify, use, and comply with voluntary and consensus standards where applicable.
ACC member companies are required to establish company

- specific goals against whic h progress is measured toward the common vision of no accidents, injuries, or harm to the environment. An example of one such goal is to limit the annual number of process safety incidents below a target level.
Member companies submit to ACC annual repor ts on process safety incidents that meet specific criteria. 61 The ACC Process Safety Code Measurement System (PSCMS), established in 1996, contains data on

61 The criteria include any fire or explosion causing more than $25,000 in property damage; an episodic loss of containment incident of a chemical in excess of the threshold quantities listed in 40 CFR 355.40, Appendix A; an episodic loss of containment incident involving more than 5,000 pounds of a flammable substance; or any fire, explosion, or chemical release that involves one or more fa talities or serious injuries.Reactives Hazard Investigation 10
- 17
- 02, page 79

type of incident (i.e., fire, explosion, toxic gas), number of injuries, etc., for 1,500 facilities

– but no data on causes of incidents or lessons learned.
PSCMS is primarily designed as a metric for tracking industry performance on process safety incidents; it is not intended to be a lessons

- learned database. However, if expanded to include causes an d lessons learned and if more widely distributed, the data could be useful in preventing similar incidents. 

### 7.1.2 SOCMA Guidance on Implementation
The Guide to Process Safety is designed to help with implementation of the Responsible Care Process Safet y Code (SOCMA, 1999). The guide presents voluntary, proactive initiatives for the continuous improvement of process safety performance.
The SOCMA process safety committee informally shares information on incidents at member facilities, but it does not of fer a formal incident reporting mechanism such as the ACC PSCMS.



## 7.2 NACD Responsible Distribution Process Reactive incidents are not unique to the chemical manufacturing industry. Approximately 30 percent of incidents in CSB data occurred at industria l facilities that use or consume chemicals in bulk quantities.
NACD is an association of chemical distributor companies that purchase and take title of chemical products from manufacturers. 62 Member companies process, formulate, blend, repackage, warehous e, transport, and market chemical products to industrial customers. NACD has developed the Responsible Distribution Process (RDP), which is similar in concept to the ACC Responsible Care code.

62 NACD has approximately 300 member companies and distributes to 750,000 industrial customers.Reactives Hazard Investigation 10
- 17
- 02, page 80

As a condition of NACD membership, each chemical distribution company is required have an active safety management program designed to continuously improve safety and reduce incidents. The RDP code has been in place since 1991 and includes risk management, compliance review and training, carrier selection, handling and storage, job procedures and training, waste management, emergency response and public preparedness, community outreach, and product stewardship.
NACD (1997) has published an RDP implementation guide to assist member companies in developing
programs. A self

- evaluation and a third

- party onsite MSV audit are required. In the last 3 years, NACD has expelled 20 companies because of noncompliance.
RDP does not contain explicit requirements for reactive hazard management, though several elements may apply . For example, the handling and storage element requires;
. . . procedures for loading and unloading chemicals at the member company’s facilities that result in protection of personnel, a reduction in emissions to the environment, and ensures that chemic als are loaded and unloaded into and out of proper storage facilities.
This element implicitly applies to reactive hazards in terms of inadvertent mixing of incompatible materials.
The RDP handling and storage element also requires “a program for provi ding manufacturer guidance and information to customers, warehouses, terminals and carriers on procedures for loading, unloading, and storing chemicals.” Again, this element implicitly applies to the communication of good practices for reactive hazards

– fr om the manufacturer to the end use customer. The product stewardship element of RDP includes similar requirements.Reactives Hazard Investigation 10
- 17
- 02, page 81



## 8.0 Alternatives for Improving Regulatory Coverage
There is considerable debate over the need to extend regulatory coverage of reactive hazards. Testimony provided at the CSB public hearing on May 30, 2002, and elsewhere indicates a general consensus that there are concerns with the number and range (i.e., addressing reactive mixtures of substances as well as single substances) of reactiv e hazards covered under the OSHA PSM Standard and EPA RMP regulation. However, there is no consensus on how the problems should be addressed

– for example, by regulatory means, by voluntary efforts such as ACC’s Responsible Care program, or by a combination of approaches.
There are significant differences in the laws authorizing the OSHA PSM Standard and the EPA RMP regulation. Because EPA specifically lists substances covered under RMP and does not establish classes of substances, this report separately d iscusses alternatives for OSHA (Section 8.1) and EPA (Section 8.2). (Section 8.3 briefly discusses regulatory relief absent catastrophic consequences, and Section 8.4 suggests improvements within the requirements of the existing PSM Standard and RMP regul ation to enhance hazard identification and hazard evaluation.)



## 8.1 Improved Coverage Under OSHA PSM
8.1.1 Highly Reactive Substance Classification One approach to improve management of reactive hazards is to extend OSHA PSM coverage to a class of “highly reactive substances,” similar to the way the existing standard defines a class of “flammable liquids or gases.” “Highly reactive substances” would include single components as well as multicomponent substances; coverage would apply to all chemical processes (as d efined by OSHA PSM). For example, a criterion based on the heat of reaction would specify coverage if the quantity exceeded aReactives Hazard Investigation 10
- 17
- 02, page 82

certain level (e.g., 100 cal/g). Alternatively, multiple criteria such as heat of reaction and total pressure may be a better indicator of reactivity.
With relevant criteria, the highly reactive substance classification would cover the most likely process deviations and inadvertent mixing scenarios leading to injury; however, it may not take into account all
process - specific cond itions, such as inadvertent mixing of unexpected chemicals or addition of an unexpected catalyzing agent.
Highly reactive substance classification could also include regulatory relief, as discussed in Section 8.3.



### 8.1.2 Coverage Based on Hazard Evaluations A performance

- based system

– rather than a list of “reactive chemicals”

– is suggested as another alternative for extending regulatory coverage of reactive hazards. Such a system would consider the risk of reactive chemicals, site

- specific (extrinsic) factor s such as siting and proximity, and conditions that create potentially reactive situations. Objective criteria such as the North American Industry Classification System (NAICS) codes, accident history, or number of employees could be used to establish cov erage. The process hazard analysis required by OSHA PSM is an example of a performance

- based approach; it allows for a variety of hazard analysis methodologies. A performance

- based system requires experts to identify and evaluate all relevant reactive ha zards of a process and to determine the complexity of the hazards analysis. If the hazard evaluation demonstrates the possibility of a catastrophic consequence, the process has regulatory coverage. This approach to hazard evaluation allows for both a com prehensive analysis and flexibility in implementation; however, if applied to reactive hazards, it requires expertise for implementation and regulatory evaluation.Reactives Hazard Investigation 10
- 17
- 02, page 83



### 8.1.3 “Safety Case” A safety case approach along the lines of the Seveso 63 requirements i

s another possible alternative for determining regulatory coverage. The safety case requires a detailed explanation of why a process is safe to operate. Again, objective criteria such as NAICS codes, thermodynamic properties, or some combination of those criteria previously discussed are used to establish coverage.
The concept of a safety case comes from the requirements of the European Union/European Community (EU/EC) Seveso Directive (82/501/EC) and, in particular, regulations that the United Kingdom and other member states used to implement that directive. United Kingdom regulations (Control of Industrial Major Accident Hazards [CIMAH], 1984; replaced by Control of Major Accident Hazards Involving Dangerous Substances [COMAH] in 1999) require that ma jor hazardous facilities produce a safety report or safety case. 64 The requirement for a safety case is initiated by a list of chemicals and a class of flammables. Like the hazard analysis approach (Section 8.1.2), experts identify the reactive hazards o f the process; if analysis shows that the proposed process is safe, it may be excluded from additional regulatory requirements.
The objective of a safety case is to demonstrate to the regulatory authority that a company is fully aware of the hazards assoc iated with its operations and that they are conducted in a safe manner, such that employees and the public are not exposed to undue risks. The regulatory authority must examine the safety case and communicate the results of its examination to the facility , usually within a “reasonable period of time.”

63 On July 9, 1976, in Meda, Italy, near Seveso, a chemical reactor incident caused a release of dioxin (TCDD), which is a highl

y toxic chemical. The regulatory requirements developed as a result of this incident are referred to as the Seveso Directive. 64 The concept of a safety case exists within the context of a licensing regime. Licensing mechanisms exist in the United State s, but compliance with workplace safety requirements is not a prerequisite for license.Reactives Hazard Investigation 10
- 17
- 02, page 84

The safety case may be prescriptive or performance based. Although this approach is comprehensive, if applied to reactive hazards, it requires that regulatory agencies have expertise to assess the adequacy of the analysis.



## 8.2 Improved Coverage Under EPA RMP Significant differences in the laws authorizing the OSHA PSM Standard and the EPA RMP regulation may affect the means by which EPA can revise coverage of processes containing reactive hazards. EPA maintain s that it is required to specifically list substances covered under RMP and cannot establish classes of substances. For this reason, EPA individually lists flammables, rather than adopting the “class” approach to flammables used by OSHA.

Two states have s uccessfully implemented or are considering a list

- based approach to address coverage of reactive hazards that affect the public. Delaware uses the same overpressurization criterion as OSHA for determining the quantity of a listed substance that is covered . New Jersey is expected to include the criterion in its revision of the Toxic Catastrophe Prevention Act ( TCPA)

. To most effectively improve reactive hazard management, coverage under the OSHA PSM Standard and the EPA RMP regulation should be more comp atible. EPA should seek the authority needed to allow it to address reactive hazard coverage in a manner compatible with any revised OSHA approach.


## 8.3 Regulatory Relief Absent Catastrophic Consequences Physical processing conditions and even small amoun ts of extraneous materials (contaminants) that may have catalytic properties affect both the rate at which energy is released from an “intended reaction” and the potential damage. For this reason, many processes

– which could be otherwise covered

– may not
pr esent a catastrophic risk to workers under reasonable worst case scenarios. Moreover, even if theReactives Hazard Investigation 10
- 17
- 02, page 85

reaction “runs away,” there may be no catastrophic injury to workers because the process is designed to handle reasonable worst case scenarios or offers effec tive passive mitigation measures, such as containment, diking, blast walls, and adequate emergency relief systems.
Regulations could encourage inherently safer design and mitigation by granting exemptions where such measures are proven to prevent catastro phic incidents.



## 8.4 Improvements in OSHA PSM and EPA RMP Requirements
8.4.1 Improved Process Safety Information The PSI element of both the OSHA PSM Standard and the EPA RMP regulation can be improved by requiring the inclusion of all existing informati on on chemical reactivity. Examples of such information are chemical reactivity test data, such as DSC, thermogravimetric analysis (TGA), or accelerating rate calorimetry; and relevant incident reports from the plant, the corporation, industry, and govern ment. OSHA and EPA should require the facility to consult such resources as Bretherick’s Handbook of Reactive Chemical Hazards , Sax’s Dangerous Properties of Industrial Materials , and computerized tools (e.g., CHETAH, The Chemical Reactivity Work Sheet).



### 8.4.2 Improved Process Hazard Analysis In both the OSHA PSM Standard and the EPA RMP regulation, the PHA element does not currently specify the factors that must be considered to effectively manage reactive hazards. Present requirements should be augmen

ted to explicitly require an evaluation of such factors as rate and quantity of heat generated; maximum operating temperature to avoid decomposition; thermostability of reactants, reaction mixtures, byproduct waste streams, and products; effect of charging rates, catalyst addition, and possible contaminants; and understanding the consequences of runaway reactions or toxic gas evolution.Reactives Hazard Investigation 10
- 17
- 02, page 86



### 8.4.3 Improved Reporting Requirements
OSHA PSM

- covered facilities are required to investigate “each incident which result ed in, or could reasonably have resulted in a catastrophic release of a highly hazardous chemical in the workplace” (29 CFR 1910.119 [m] [1]). At the conclusion of an incident investigation, the company is required to prepare a report on the factors that contributed to the incident. At present, OSHA does not require submittal of these incident reports. However, mandatory submission of the reports would increase available data and thus improve the capability of identifying or tracking reactive incidents.


## 8.5 Regulatory Initiatives Under Review by New Jersey The New Jersey Department of Environmental Protection and Energy is presently considering amendment of its TCPA to establish coverage of reactive hazards that might affect the public. The State has as ked for stakeholder input on the following proposition (paraphrased):
Processes having a reactive hazard with a heat of reaction of 100 calories per gram will be regulated under the NJ TCPA when the quantity of reactive hazard contained in the process
equa ls or exceeds the threshold quantity calculated to result in a 2.3 psi overpressure wave endpoint at a distance of 100 meters or a lesser distance to the source boundary.
New Jersey is also considering whether it should have varying compliance requirements for covered processes. Less stringent requirements are proposed for covered processes where the reactive hazard substance is only stored in shipping containers and handled, with no emptying or filling. The State is proposing that a covered process could escape regulation under TCPA if the facility provides evidence that the reactive hazard substance is not capable of producing an explosion or deflagration overpressure.Reactives Hazard Investigation 10
- 17
- 02, page 87



## 9.0 Conclusions

1. Reactive incidents are a significant chemical safety problem.
2 The OS HA PSM Standard has significant gaps in coverage of reactive hazards because it is based on a limited list of individual chemicals with inherently reactive properties.

3. NFPA instability ratings are insufficient as the sole basis for determining coverage of reactive hazards in the OSHA PSM Standard.

4. The EPA Accidental Release Prevention Regulations (40 CFR 68) have significant gaps in coverage of reactive hazards.

5. Using lists of chemicals is an inadequate approach for regulatory coverage of reactive hazards

. Improving reactive hazard management requires that both regulators and industry address the hazards from combinations of chemicals and process

- specific conditions rather than focus exclusively on the inherent properties of individual chemicals.

6. Reactiv e incidents are not unique to the chemical manufacturing industry. They also occur in many other industries where chemicals are stored, handled, or used.

7. Existing sources of incident data are not adequate to identify the number, severity, and causes o f reactive incidents or to analyze incident frequency trends.

8. There is no publicly available database for sharing lessons learned from reactive incidents.

9. Neither the OSHA PSM Standard nor the EPA RMP regulation explicitly requires specific hazards, such a s reactive hazards, to be examined when performing a process hazard analysis. Given that reactive incidents are often caused by inadequate recognition and evaluation ofReactives Hazard Investigation 10
- 17
- 02, page 88

reactive hazards, improving reactive hazard management involves defining and requiring relevant factors (e.g., rate and quantity of heat and gas generated) to be examined within a process hazard analysis.

10. The OSHA PSM Standard and the EPA RMP regulation do not require the use of multiple sources when compiling process safety informatio n.

11. Publicly available resources 65 are not always used by industry to assist in identifying reactive hazards.

12. There is no publicly available database to share reactive chemical test information.

13. Current good practice guidelines on how to eff ectively manage reactive hazards throughout the life cycle 66 of a chemical manufacturing process are neither complete nor sufficiently explicit.

14. Given the impact and diversity of reactive hazards, optimum progress in the prevention of reactive incident s requires both enhanced regulatory and nonregulatory programs.

65 NOAA’s The Chemical Reactivity Worksheet, ASTM’s CHETAH, and Bretherick’s Database of Reactive Chemical Hazards. 66 “ Life cycle” refers to all phases of a chemica l manufacturing process

– from conceptualization, process R&D, engineering design, construction, commissioning, commercial operation, and major modification to decommissioning.Reactives Hazard Investigation 10
- 17
- 02, page 89



## 10.0 Recommendations
Occupational Safety and Health Administration (OSHA)
1. Amend the Process Safety Management Standard (PSM), 29 CFR 1910.119, to achieve more comprehensive control of re active hazards that could have catastrophic consequences. (2001

- 01

- H

- R1)

• Broaden the application to cover reactive hazards resulting from process

- specific conditions and combinations of chemicals. Additionally, broaden coverage of hazards from self

- react ive chemicals. In expanding PSM coverage, use objective criteria. Consider criteria such as the North American Industry Classification System (NAICS), a reactive hazard classification system (e.g., based on heat of reaction or toxic gas evolution), incid ent history, or catastrophic potential.

• In the compilation of process safety information, require that multiple sources of information be sufficiently consulted to understand and control potential reactive hazards. Useful sources include:

- Literature sur veys (e.g., Bretherick’s Handbook of Reactive Chemical Hazards, Sax’s Dangerous Properties of Industrial Materials ).

- Information developed from computerized tools (e.g., ASTM’s CHETAH, NOAA’s The Chemical Reactivity Worksheet).Reactives Hazard Investigation 10
- 17
- 02, page 9 0

- Chemical reactivity test da ta produced by employers or obtained from other sources (e.g., differential scanning calorimetry, thermogravimetric analysis, accelerating rate calorimetry).

- Relevant incident reports from the plant, the corporation, industry, and government.

- Chemical Abs tracts Service.

• Augment the process hazard analysis (PHA) element to explicitly require an evaluation of reactive hazards. In revising this element, evaluate the need to consider relevant factors, such

as:

- Rate and quantity of heat or gas generated.

- Maxi mum operating temperature to avoid decomposition.

- Thermal stability of reactants, reaction mixtures, byproducts, waste streams, and products.

- Effect of variables such as charging rates, catalyst addition, and possible contaminants.

- Understanding the conseq uences of runaway reactions or toxic gas evolution.

2. Implement a program to define and record information on reactive incidents that OSHA investigates or requires to be investigated under OSHA regulations. Structure the collected information so that it can be used to measure progress in the prevention of reactive incidents that give rise to catastrophic releases. (2001

- 01

- H

- R2)Reactives Hazard Investigation 10
- 17
- 02, page 91



### U.S. Environmental Protection Agency (EPA)
1. Revise the Accidental Release Prevention Requirements, 40 CFR 68, to explicitl y cover catastrophic reactive hazards that have the potential to seriously impact the public, including those resulting from self

- reactive chemicals and combinations of chemicals and process

- specific conditions. Take into account the recommendations of thi s report to OSHA on reactive hazard coverage. Seek congressional authority if necessary to amend the regulation. (2001

- 01

- H

- R3)

2. Modify the accident reporting requirements in RMP* Info to define and record reactive incidents. Consider adding the term “ reactive incident” to the four existing “release events” in EPA’s current 5

- year accident reporting requirements (Gas Release, Liquid Spill/Evaporation, Fire, and Explosion). Structure this information collection to allow EPA and its stakeholders to ident ify and focus resources on industry sectors that experienced the incidents; chemicals and processes involved; and impact on the public, the workforce, and the environment. (2001

- 01

- H

- R4)


### National Institute of Standards and Technology (NIST) Develop and

implement a publicly available database for reactive hazard test information. Structure the system to encourage submission of data by individual companies and academic and government institutions that perform chemical testing. (2001

- 01

- H

- R5)


### Center for Chemical Process Safety (CCPS)

1. Publish comprehensive guidance on model reactive hazard management systems. (2001

- 01

- H

R6) At a minimum, ensure that these guidelines cover:Reactives Hazard Investigation 10
- 17
- 02, page 92

• For companies engaged in chemical manufacturing: reactive hazard management, including hazard identification, hazard evaluation, management of change, inherently safer design, and adequate procedures and training.

• For companies engaged primarily in the bulk storage, handling, and use of chemicals: identification and prevention of r eactive hazards, including the inadvertent mixing of incompatible substances.

2. Communicate the findings and recommendations of this report to your membership. (2001

- 01

- H

R7)


### American Chemistry Council (ACC)
1. Expand the Responsible Care Process Safe ty Code to emphasize the need for managing reactive hazards. (2001

- 01

- H

- R8) Ensure that:

• Member companies are required to have programs to manage reactive hazards that address, at a minimum, hazard identification, hazard evaluation, management of change, inherently safer design, and adequate procedures and training.

• There is a program to communicate to your membership the availability of existing tools, guidance, and initiatives to aid in identifying and evaluating reactive hazards.

2. Develop and impleme nt a program for reporting reactive incidents that includes the sharing of relevant safety knowledge and lessons learned with your membership, the public, and government to improve safety system performance and prevent future incidents. (2001

- 01

- H

- R9)Reactives Hazard Investigation 10
- 17
- 02, page 93

3. Work with NIST in developing and implementing a publicly available database for reactive hazard test information. Promote submissions of data by your membership. (2001

- 01

- H

- R10)

4. Communicate the findings and recommendations of this report to your memb ership. (2001

- 01

- H

- R11)


### Synthetic Organic Chemical Manufacturers Association (SOCMA)
1. Expand the Responsible Care Process Safety Code to emphasize the need for managing reactive hazards. (2001

- 01

- H

- R12) Ensure that:

• Member companies are required to hav e programs to manage reactive hazards that address, at a minimum, hazard identification, hazard evaluation, management of change, inherently safer design, and adequate procedures and training.

• There is a program to communicate to your membership the availa bility of existing tools, guidance, and initiatives to aid in identifying and evaluating reactive hazards.

2. Develop and implement a program for reporting reactive incidents that includes the sharing of relevant safety knowledge and lessons learned with y our membership, the public, and government to improve safety system performance and prevent future incidents. (2001

- 01

- H

- R13)

3. Work with NIST in developing and implementing a publicly available database for reactive hazard test information. Promote sub missions of data by your membership. (2001

- 01

- H

- R14)

4. Communicate the findings and recommendations of this report to your membership. (2001

- 01

- H

- R15)Reactives Hazard Investigation 10
- 17
- 02, page 94



### National Association of Chemical Distributors (NACD)
1. Expand the existing Responsible Distribution P rocess to include reactive hazard management as an area of emphasis. At a minimum, ensure that the revisions address storage and handling, including the hazards of inadvertent mixing of incompatible chemicals. (2001

- 01

- H

- R16)

2. Communicate the findings and recommendations of this report to your membership. (2001

- 01

- H

- R17)


### International Association of Firefighters Communicate the findings and recommendations of this report to your membership. (2001

- 01

- H

- R18) 

### Paper, Allied - Industrial, Chemical & Energy Workers International Union (PACE) Communicate the findings and recommendations of this report to your membership. (2001

- 01

- H

- R19)


### The United Steelworkers of America Communicate the findings and recommendations of this report to your membership. (2001

- 01

- H

- R20) 

### Union of Needletrades, Industrial, and Textile Employees (UNITE) Communicate the findings and recommendations of this report to your membership. (2001

- 01

- H

- R21)


### United Food and Commercial Workers International Union Communicate the findings an d recommendations of this report to your membership. (2001

- 01

- H

- R22) 

### American Society of Safety Engineers (ASSE) Communicate the findings and recommendations of this report to your membership. (2001

- 01

- H

- R23)Reactives Hazard Investigation 10
- 17
- 02, page 95



### American Industrial Hygiene Association (AIH A) Communicate the findings and recommendations of this report to your membership. (2001

- 01

- H

- R24)

By the U.S. Chemical Safety and Hazard Investigation Board

Carolyn W. Merritt Chair
John S. Bresland Member Gerald V. Poje, Ph.D. Member
Isadore Ro senthal, Ph.D. Member Andrea Kidd Taylor, Dr. P.H. Member
October 8, 2002Reactives Hazard Investigation 10
- 17
- 02, page 96



## 11.0 References
American Chemistry Council (ACC), 2001. Responsible Care: Good Chemistry at Work

. Barton, John, and Richard Rogers, 1997. Chemical Reaction Hazards, A Gui de to Safety, Rugby, U.K.: Institution of Chemical Engineers (IChemE). Bretherick, Leslie, P. G. Urben, and Martin J. Pitt, 1999. Bretherick’s Handbook of Reactive Chemical Hazards, Sixth Edition, Vol. 1, Butterworth

- Heinemann.
Center for Chemical Proc ess Safety (CCPS), 2001. Safety Alert, Reactive Material Hazards , American Institute of Chemical Engineers (AIChE). CCPS, 1995a. Guidelines for Chemical Reactivity Evaluation and Application to Process Design, AIChE. CCPS, 1995b , Guidelines for Safe Sto rage and Handling of Reactive Materials , AIChE. CCPS, 1992. Guidelines for Hazard Evaluation Procedures , 2 nd Edition With Worked Examples , AIChE. CCPS, 1989. Technical Management of Chemical Process Safety, AIChE. Chemical Manufacturers Association (now American Chemistry Council [ACC]), 1989. Process Safety Code

. CONSAD Corporation, 1998. Analytical Support and Data Gathering for an Economic Analysis of the Addition of Selected Reactive Chemicals Within the Scope of the OSHA Process Safety Management Standard , December 15, 1998. HarsBook, 2001. Thematic Network on Hazard Assessment of Highly Reactive Systems (HarsNet), BET2

- 0572, Industrial and Materials Technologies Programme of the European Commission. Health and Safety Executive (HSE), 2000. Desi gning and Operating Safe Chemical Reaction Processes, Rugby, U.K.: HSE Books. Hofelich, T. C., B. A. Prine, and N. E. Scheffler, 1997. “A Quantitative Approach to Determination ofReactives Hazard Investigation 10
- 17
- 02, page 97

NFPA Reactivity Hazard Rating Parameters,” Process Safety Progress , Vol. 16 , No. 3, Fall 1997, pp. 121

- 125. Grewer, T., 1994. Thermal Hazards of Chemical Reactions, Industrial Safety Series, Vol. 4, Elsevier Science. Koseki, Hiroshi, and Y. Iwata, 2001. “Study on Risk Evaluation of Hydroxylamine/Water Solution,” Proceedings, Be yond Regulatory Compliance, Making Safety Second Nature , Mary Kay O’Connor Process Safety Center, Texas A&M University, October 2001. Lewis, Richard J., 1996. Sax’s Dangerous Properties of Industrial Materials , Ninth Edition, Van Nostrand Reinhold.
Melh am G.A., and E.S. Shanlet, 1995. “On the Estimation of Hazard Potential for Chemical Substances,” International Symposium on Runaway Reactions and Pressure Relief Design, AIChE. National Association of Chemical Distributors (NACD), 2002. Responsible Dist ribution Process Code of Management Practice , April 2002. National Fire Protection Association (NFPA), 2001a. Fire Protection Guide to Hazardous Materials , 13 th edition. NFPA, 2001b. System for the Identification of the Hazards of Materials for Emergenc y Response , NFPA 704. NFPA, 1994. Hazardous Chemical Data , NFPA 49. National Transportation Safety Board (NTSB), 2000. Hazardous Materials Accident Brief, Whitehall, Michigan, Chemical Reaction During Cargo Transfer , June 4, 1999. Occupational Safety an

d Health Administration (OSHA), 1996. Hazard Information Bulletin, Water Reactive Chemicals, Hazardous Materials Not Covered Under 29 CFR 1910.119 , July 3, 1996. Pohanish, Richard P., and Stanley A. Greene, 1997. Rapid Guide to Chemical Incompatibilities , John Wiley & Sons, Inc. Stoessel, F., 1993. “What is Your Thermal Risk?” Chemical Engineering Progress , AIChE, OctoberReactives Hazard Investigation 10
- 17
- 02, page 98

1993. Synthetic Organic Chemical Manufacturers Association (SOCMA), 1999. Guide to Process Safety, 2 nd Edition.
United Nations 1999. Recommendations on the Transport of Dangerous Goods, Test and Criteria (the Orange Book), 3 rd Edition

. U.S. Chemical Safety Board (USCSB), 2002a. Case Study, The Explosion at Concept Sciences: Hazards of Hydroxylamine, No. 1999

- 13

- C

- PA, March 2002.
USCS B, 2002b. Investigation Report, Thermal Decomposition Incident, BP Amoco Polymers, Inc., Augusta, Georgia, March 13, 2001 , No. 2001

- 03

- I

- GA, June 2002. USCSB, 2001. Safety Bulletin, Management of Change, No. 2001

- 04

- SB, August 2001. USCSB, 2000. Investi gation Report, Chemical Manufacturing Incident, Morton International, Inc., Paterson, New Jersey, April 8, 1998 , N o . 1998

- 06

- I

- NJ. U.S. Environmental Protection Agency (USEPA), 2000. “Case Study: Waste Fuel/Oxidizer Reaction Hazards,” Prevention of React ive Chemical Explosions, EPA 550

- F00

- 001, Office of Solid Waste and Emergency Response, April 2000. USEPA, 1999. “Case Study: Phenol

- Formaldehyde Reaction Hazards,” How to Prevent Runaway Reactions, EPA

- 550

- F99

- 004, Office of Solid Waste and Emergency Re sponse, August 1999. USEPA, 1997. Explosion Hazards From Ammonium Nitrate, EPA 550

- F97

- 002d, Office of Solid Waste and Emergency Response, December 1997.
USEPA

- Occupational Safety and Health Administration (OSHA), 1999. Joint Chemical Accident Investigat ion Report on BPS , Inc., West Helena, Arkansas, April 1999.
USEPA

- OSHA, 1997. Joint Chemical Accident Investigation Report , Napp Technologies, Inc., Lodi, New Jersey, October 1997.Reactives Hazard Investigation 10
- 17
- 02, page 99



## APPENDIX A: Glossary
Adiabatic calorimetry: Chemical testing te chniq ue that determines the self

- heating rate and pressure data of a chemical under near

- adiabatic conditions. (“Adiabatic” refers to any change in which there is no gain or loss of heat.) This measurement technique conservatively estimates the conditions for , and consequences of, a runaway reaction.

Acid
- base reaction: Chemical reaction involving the transfer of a hydrogen ion from an acidic substance to a basic substance.

Blast: Potentially damaging pressure or shock wave produced by an explosion.
Catalyst: Substance that usually increases the rate of a chemical reaction without changing its own composition.
Chemical incompatibility : Type of reactive hazard that occurs when a chemical is mixed or comes in contact with other chemicals, or process materi als, resulting in an uncontrolled and often violent reaction.

Chemical reaction: Interaction of substances in which they undergo change of composition and properties due to changes in molecular structure of the constituent atoms or molecular fragments.

Ch lorination: Reaction of substances with chlorine whereby chlorine atoms are chemically integrated into the original chemical molecule.

Contaminant:

Any substance that enters a process where it is not normally found.
Decomposition: Chemical reaction tha t leads to the breakdown or decomposition of a chemical into smaller molecules or elements, often with the liberation of energy and product gases.Reactives Hazard Investigation 10
- 17
- 02, page 100

Differential scanning calorimetry (DSC): Chemical testing technique that is used to establish approximate te mperature ranges in which a substance undergoes an exothermic decomposition and to determine the energy output of those reactions; may also be used to study endothermic processes, such as melting. DCS data provide very simple and approximate reaction kine tics.
Differential thermal analysis (DTA): Chemical testing technique that produces similar data to DSC. DTA uses temperature differences to generate test results; DSC has largely replaced the DTA technique as a screening tool for obtaining chemical haza rd test data.

Endothermic reaction: Chemical reaction that absorbs heat.
Explosion: Sudden release of energy that causes a blast or shock wave; may lead to personal injury or structural damage.

Exothermic reaction: Chemical reaction that liberates hea t.
Halogenation: Chemical reaction of substances with a halogen

– typically, fluorine, chlorine, and bromine. See “chlorination.”
Hazard: Chemical or physical condition that has the potential to cause harm to human life, property, or the environment.

Haz ard evaluation: Systematic process to investigate hazards, assess potential consequences, and establish a design and operating basis for safety.
Hazard and operability analysis (HAZOP): A qualitative hazard analysis technique to identify and evaluate pro

cess hazards and potential operating problems; focuses on a detailed and systematic examination of process deviations and their consequences.Reactives Hazard Investigation 10
- 17
- 02, page 101

Human factors:

Discipline concerned with designing machines, operations, and work environment to match human capa cities and limitations.
Hydrolysis: Chemical reaction of a substance with water; may lead to undesired runaway reactions and generation of gaseous molecules, such as hydrogen, hydrogen chloride, and alkanes.
Impact or thermally sensitive material: Mate rial that decomposes rapidly when subjected to heat or impact, resulting in a potentially explosive release of energy.
Layers of protection: Multiple, redundant, or diverse safeguards to prevent an incident from occurring regardless of the initiating even t or the performance of any single safeguard.
Management system: Structured, systematic method to implement an identified set of activities with assigned responsibilities and accountability.
Mixing calorimetry: Technique used to measure heat evolved upon instantaneous mixing of two or more chemicals; usually designed to be rapid (15 to 45 minutes), operating over the range of

- 50 to 200 degrees Celsius (°C).

Monomers: Chemicals that are the simple starting units from which polymers are made; they are re active and sometimes unstable under ambient conditions.

Nitration: Chemical reaction of a substance in which the nitro group (

- NO 2 ) is introduced into the molecule; often accomplished under highly reactive conditions using mixtures of nitric and sulfuric acids at high temperatures. Byproducts of the reaction may have explosive properties; if reaction control is lost, may lead to vigorous and strongly exothermic runaway reactions due to oxidation of the reactants.

Oxidation: Chemical reaction in which t he oxidation state of a molecule increases due to the abstractionReactives Hazard Investigation 10
- 17
- 02, page 102

of electrons; often occurs when oxygen or other oxidizing material combines with the reacting substance.

Oxidation
- reduction (REDOX): Chemical reaction in which an element loses (oxidation) or gains (reduction) an electron.
Oxidizer: Material that readily yields oxygen or other oxidizing gas, or that readily reacts to promote or initiate combustion.
Polymer: Large chemical molecule made up of repeating smaller units (e.g., polyethylene i s a synthetic polymer made up of repeating ethylene units).
Polymerization: Chemical reaction in which one or more relatively simple molecules (monomers) combine to form a more complex compound (polymer).
Process hazard analysis: Organized effort to ide ntify and evaluate hazards associated with chemical processes; normally involves the use of qualitative techniques to identify and assess the significance of hazards.

Process - specific factors: Conditions such as temperature, pressure, quantities handled, chemical concentrations, catalytic effects, and addition rates.
Process life cycle: All phases of a process from its conception through chemical and process research and development (R&D), engineering design, construction, commissioning, commercial operat ion, major modification, and decommissioning.

Public: Any person other than employees or contractors at or near a facility.
Public impact: Known injury to the public, offsite evacuation, or shelter

- in

- place.Reactives Hazard Investigation 10
- 17
- 02, page 103

Reactive incident:

Sudden event involving a n uncontrolled chemical reaction

– with significant increases in temperature, pressure, or gas evolution

– that has caused, or has the potential to cause, serious harm to people, property, or the environment.
Reactive chemical process safety: Systematic ident ification, evaluation, and control of reactive hazards at all phases of the production life cycle

– from R&D to pilot plant, change management, and decommissioning; and for all types of operations

– from storage or manufacturing to packaging or waste processin g.
Reactive hazard: Reactive properties and physical conditions of a single chemical or mixture that have the potential to generate heat, energy, and gaseous byproducts that have the potential to do harm.
Reactivity: Tendency of substances to undergo c hemical change.
Reaction calorimetry: Chemical testing te chnique that determines thermodynamic and kinetic information on a desired reaction under conditions closely similar to those of a larger

- scale plant; measures heat flow (production of desired proc ess) and product generation (without knowledge of heat of reaction), and facilitates isothermal and temperature

- ramped experiments.

Root cause: Primary reason why an incident occurred, developed through systematic analyses.
Runaway reaction: Reaction tha t is out of control because the heat generation rate exceeds the rate at which heat is removed to cooling media and surroundings.
Self
- reactivity: Chemical reaction that involves only one chemical substance.
Thermal gravitational analysis (TGA): Chemic al testing technique that precisely measures weight loss (due to gas forming reactions) as a function of temperature and time.Reactives Hazard Investigation 10
- 17
- 02, page 104

Toll manufacturer: Facility that blends, mixes, processes, or packages chemicals.

Worst case scenario: The most severe postula ted scenario involving an uncontrolled reaction.

Water reactive: Substance that reacts with water, often producing a vigorous exothermic reaction

.Reactives Hazard Investigation 10
- 17
- 02, page 105



## APPENDIX B: Surveys

B.1 Industry Survey The U.S. Chemical Safety and Hazard Investigation Board (CSB) co nducted a survey of companies that store, handle, and process chemicals. The objective of the survey was to examine current management practices with regard to reactive hazard management. Survey responses served primarily to highlight good practices, but

also to point out areas for potential improvement. The survey questionnaire is posted on the CSB website at http://www.chemsafety.gov/info/Reactives.Survey.Final.pdf.
The survey was designed, administered, and analyzed by CSB staff with the support of EQE International, a consulting company with expertise in chemical process safety. Questions focused on the application of systematic programs, procedures, and practices for reactiv e chemicals management at the site level. Respondents were asked to provide details about good management practices in all phases of the manufacturing life cycle, including research and development (R&D), engineering, capital projects, commissioning, plan

t operations, and management of change (MOC). Where possible, respondents were asked to provide information about actual, routine practices.
The nine surveyed companies volunteered to participate. Industry trade associations (American Chemistry Council [ ACC], National Association of Chemical Distributors [NACD], Synthetic Organic Chemical Manufacturers Association [SOCMA]) and professional societies (Center for Chemical Process Safety [CCPS]) were asked to identify possible survey candidates

– small, medium , and large sites or companies with reactive chemical hazard management programs or practices in place. As such, the survey was not intended to represent the practices of the chemical industry as a whole; in fact, the surveyReactives Hazard Investigation 10
- 17
- 02, page 106

respondents more likely repr esent the “upper tier” of companies/facilities handling reactive chemicals and managing the related hazards.
To supplement the industry survey, CSB staff conducted five selected site visits at industry facilities that have implemented programs for managing reactive hazards. The first

- hand information gathered in these visits provided an understanding of the challenges involved in developing a systematic management program for reactive hazards.
All nine survey participants were primarily engaged in chemical manufacturing, representing synthetic organic chemicals, pharmaceuticals, specialty chemicals, fine organics, polymers, agrochemicals, and contract manufacturing. Most considered their site to use many reactive chemicals and highly reactive chemicals. I nterpretation of the term “highly reactive” was left to the participant. Seven of the nine survey respondents were member companies of ACC; four of nine were member companies of SOCMA; and five of nine were CCPS sponsors.
Considering the limitations of the industry survey

– including the small number of respondents

– it is important to correspondingly recognize that the conclusions are also limited. Although representative small, medium, and large companies and sites were surveyed, the conclusions of this i nvestigation do not support a differentiation among the practices of small versus large companies.



## B.2 SOCMA Survey SOCMA conducted a survey of members during its April 2001 Responsible Care Conference on Managing Reactive Chemicals. However, eight of t he 10 respondents represented facilities with less than 100 employees.Reactives Hazard Investigation 10
- 17
- 02, page 107



## APPENDIX C: Site Visits

C.1 Company Profiles Company A is a major pharmaceutical manufacturer with worldwide operations. The U.S. Chemical Safety and Hazard Investigation Board (C SB) staff visited a site with both pilot

- plant facilities and pharmaceutical manufacturing operations. The company is continually developing new and innovative chemistry, which results in frequent changes in the chemicals handled and manufacturing techniq ues used.
Company B is a diversified chemical manufacturing company with worldwide operations. CSB staff visited the corporate headquarters, which also houses extensive chemical manufacturing operations. The site also has an extensive thermal hazards t esting capability. CSB met with corporate staff, site manufacturing personnel, and thermal hazards chemists. The Company B testing laboratory evaluates a range of chemicals.
Company C is a small custom chemical manufacturer. Contract manufacturing acc ounts for its entire business. CSB staff visited a small manufacturing site with several batch chemical manufacturing operations. The nature of custom chemical manufacturing translates into very frequent changes in chemicals handled and processed.
Compan y D is a large pharmaceutical manufacturer with worldwide operations. CSB staff visited a pilot

plant facility and thermal hazards laboratory. Pilot

- plant operations included the use of several batch chemical reactors. Like Company A, this company also frequently changes chemicals handled and manufacturing techniques.Reactives Hazard Investigation 10
- 17
- 02, page 108

Company E is a large chemical manufacturer with worldwide operations. CSB staff visited a medium

sized manufacturing site. Operations included storage and handling/processing of monomers , as well as extensive batch polymerization. The site uses standardized manufacturing methods and typically handles a specific set of chemicals.


## C.2 Analysis of Practices for Reactive Chemical Hazard Management

C.2.1 Company A (Major Pharmaceutical Man facturer) C.2.1.1 Program Philosophy

• Reactive chemical hazard management is one element of an overall process safety program, but is emphasized through thermal hazards analysis.

• Capabilities and practices are driven by the business need for rapid scaleu p and high product quality.

• The corporate environmental health and safety (EHS) group provides technical resources (including expertise in reactive chemicals).

• The corporate research and development (R&D) facility has sophisticated thermal hazards capabili ty/expertise.


### C.2.1.2 Hazard Identification and Testing Program

• The company employs a phased approach to identify hazards, as outlined below:Reactives Hazard Investigation 10
- 17
- 02, page 109

Company A, Hazard Identification Stage Activity

Research Literature search
Pilot plant (process development) Screening test prior to pilot plant

Production Additional tests as indicated by process hazard analysis (PHA)

• Scaleup to pilot plant is the key step in identifying and controlling reactivity hazards.

• A checklist approach is used to gather process safet y information (PSI) prior to scaleup to pilot plant.

- Basic process/chemical data

– material safety data sheet (MSDS), special handling requirements, pressure, temperature, gaseous byproducts, and waste streams; includes a list of potentially hazardous chemic al interactions.

- Reaction safety

– thermal test data, hazardous bond groups, and exothermic reactions.

- Powder handling/milling

– dust explosion issues.

• The company is beginning to use chemical interaction matrices as an input to PHA review.

• The company has a w ell

- equipped laboratory for thermal hazards screening and sophisticated reaction calorimetry.Reactives Hazard Investigation 10
- 17
- 02, page 110

• Small quantities and the high cost of making the product limit the amount of material available for R&D testing.

• Differential scanning calorimetry (DSC) and du st explosion tests are usually conducted before a new chemical goes into the pilot

- plant phase.

• Thermal hazards data are accessible through the company intranet.



### C.2.1.3 Hazard Evaluation

• The company conducts process hazards evaluation of all new or mod ified products/processes.

• PHA techniques involve a combination of “what if” for unit operations and hazard and operability (HAZOP) for both equipment

- and procedural

- based deviations.

• Thermal hazards testing staff play a key role on the PHA team.

• The t hermal hazards laboratory, in consultation with pilot

- plant engineering, typically assess emergency venting scenarios and requirements for runaway reaction hazards.

• Over 1,300 equipment configuration changes per year account for extensive use of
managemen

t of change (MOC).



### C.2.1.4 Risk Reduction/Controls

• PHA forms the basis for identifying needed controls.

• Small

- scale batch equipment is typically “over designed” for multipurpose use.Reactives Hazard Investigation 10
- 17
- 02, page 111

• The company has in place numerous checks and balances to prevent huma n error; quality assurance (QA)

- driven processes require validation (secondary checks/rechecks) of operator actions, sampling/analysis, etc.


### C.2.1.5 Communications and Training

• The pharmaceutical industry has no official EHS trade group that develops c odes of practice equivalent to Responsible Care.

• The company recognizes the need for better and more formal sharing of lessons learned and for support of an improved industry incident database.



### C.2.2 Company B (Diversified Chemical Manufacturer)
C.2.2 .1 Program Philosophy

• The reactives program focuses on preventing uncontrolled chemical reactions that have the potential to cause loss or injury or environmental harm.

• Reactive hazards are addressed separately and uniquely from other process safety fa ctors.

• The reactives program involves the interaction of several diverse technical experts to study the chemistry and process, looking for risk reduction opportunities; in

- house expertise is available to handle reactive chemical issues.

• The company perceiv es its reactives program as adding value rather than being regulatory driven.Reactives Hazard Investigation 10
- 17
- 02, page 112

• Value is defined as having a competitive advantage; reducing damage to the facility, property, and equipment; reducing injuries; and being accepted as a good member of the

commu nity.

• The company advocates an outside

- in approach, using reviewers from outside the technology or business to help identify hazards that may h ave been overlooked.

• Program philosophy focuses on identifying potential accident scenarios.

• The reactives progr am emphasizes both self

- reactivity (instability) and binary reactivity.

• The company strongly supports owner responsibility on the part of the production leader

– knowing reactive chemicals and their process hazards, participating in the establishment and mai ntenance of corporate memory, and demonstrating a fundamental understanding of reactive chemical hazards within the facility within 90 days of any new assignment.

• Corporate guidelines require that individuals develop an understanding of reactive hazards ba sed on data collection, hazard evaluation, training, etc.

• Corporate standards, approved by the EHS board, are established for audit/review; performance

- based training; MOC, which is approved by the area production leader; and training, which addresses wors t case scenarios, cardinal rules, and lines of defense.

• There are corporate guidelines for application of the reactive chemicals program, formation of a reactive chemicals team, project reviews, and chemicals testing.Reactives Hazard Investigation 10
- 17
- 02, page 113

• Key deliverables are capital project reviews; new production leader reviews; existing facility hazard reviews on a 3

-

to 5

- year cycle; research facility reviews; and a formal training and
awareness program.

• The company offers as key resources a global standard, how

- to guidelines, testing labo ratories/expertise, and computerized tools for review.

• The company offers multidisciplinary support through research, manufacturing, 27 technology centers, and EHS.

• Technology centers provide critical functions in establishing corporate memory, documenti ng findings and implementing preventive measures, submitting data to CCPS, sharing operating knowledge across the company, and establishing effective process technologies.


### C.2.2.2 Hazard Identification and Testing Program

• Key elements of reactive hazard identification are owner

- initiated review, chemistry review, review of unit operations, review of scenarios, definition of required testing, records testing, and interpretation of results for owner.

• Testing centers are geographically distributed and includ e contractor support.

• Testing includes screening (e.g., literature research, mixing calorimetry, thermodynamic calculations, estimation of heats of reaction, DSC, flash point calculations), quantitative assessment (e.g., accelerated rate calorimetry, speci alized calorimetry), and scaleup (vent size packaging [VSP], modeling, reaction calorimetry).Reactives Hazard Investigation 10
- 17
- 02, page 114

• The program focuses on binary and higher levels of reactivity in addition to self

- reactivity (instability).

• An incompatibility

- mixing chart facilitates the predi ction of reactive mixing hazards.

• The reactive testing laboratories cover fire, dust, kinetics, high energy, and thermodynamics.



### C.2.2.3 Hazard Evaluation

• The company hazard review process was revised in June 1997 to combine reactive chemicals, loss p revention, distribution risk review, EHS review for safety and loss, project risk review, and technology center review.

• Each major company site has a hazard review committee to administer the standard and guideline. The committee includes representatives from process safety, chemistry, reactive chemistry, manufacturing, process engineering, pilot

- plant operations, and the technology
center.

• The outside

- in approach brings people without specific knowledge of a process into reviews.

• Flowcharts are used for p rocess overview; analysis of causes and consequences, lines of defense, and testing data requirements; and review of hazard checklist, schedule, and followup on recommendations.

• Review of work progress includes scenarios for inadvertent mixing, reaction lo ss - of

- control, and instability of materials.Reactives Hazard Investigation 10
- 17
- 02, page 115



### C.2.2.4 Risk Reduction/Controls

• The need for additional controls is identified through design standards, reactive chemicals process hazard analysis, and technology centers.



### C.2.2.5 Communications and Tra ining

• The communications/training challenge is to retain learning from incidents in corporate memory to prevent recurrence.

• The key premises of corporate memory are to never have to pay for an incident more than once, to learn from history and leverage acr oss all plants and technologies, and to derive benefit from the experience of other companies.

• Eighty percent of incidents are due to known chemistry hazards; it has been 6 years since the company’s last “unknown” chemistry incident.

• Technical centers pro vide small sites access to data and technical expertise for reactive chemicals.

• The company maintains global databases for 60,000+ tests, prior incident data for 22 years, and databases of all credible reactive chemical scenarios with key lines of defense for all technologies.

• Small sites generally have little/no capability in R&D, process engineering, reactive chemical testing, and chemistry.

• A global reactive chemical newsletter is published regularly and read by over 4,000 employees worldwide.Reactives Hazard Investigation 10
- 17
- 02, page 116



### C.2.3 C ompany C (Custom Chemical Manufacturer) C.2.3.1 Program Philosophy

• Management considers reactive hazard management as a subset of process safety management.

• The company has specific procedures for reactive chemicals hazard management.

• Management takes a proactive approach in terms of Occupational Safety and Health Administration (OSHA) and U.S. Environmental Protection Agency (EPA) requirements. The company applies the PSM Standard and the Risk Management Program (RMP) regulation to processes that normall y do not require coverage (under threshold quantities) because it makes good business sense.

• Management focuses on safety

- oriented programs to prevent business interruptions.

• Reactive hazards play a significant role in deciding whether to manufacture new c hemicals onsite.

• Although the company has very limited safety resources onsite, management perceives safety as added value and hires individuals from organizations with a good safety culture. The management commitment to safety is clearly evident in each aspect of the safety program.

• When a customer requests production of a chemical, the steering committee reviews the inquiry and determines the initial feasibility of production; within 1 to 2 weeks, the committee renders a go

- no go decision to the custome r. Process safety plays a significant role in the decision process.Reactives Hazard Investigation 10
- 17
- 02, page 117



### C.2.3.2 Hazard Identification and Testing Programs

• The customer requesting production of a chemical provides reactive hazard information (literature reviews, thermal test data, etc.).

• If the information is insufficient to assess reactive hazards, additional data are requested, such as thermal screening test data.

• When considering development of a new process for a customer, a team is formed to assess potential hazards (including reac tive) and to determine the technically feasibility of production.

• Potential hazards (flammability, corrosivity, etc.) are reviewed to identify concerns regarding the storage and handling of reactive chemicals, and information is obtained from raw materi al suppliers (e.g., technical bulletins). Flashpoint, DSC, or differential thermal analysis (DTA) testing is typically done by the customer.

• If potential reactive hazards are identified within a proposed process, the customer is asked to provide additiona l test data. The company only occasionally contracts testing services.



### C.2.3.3 Hazard E v aluation

• Expert opinion is essential in the hazard evaluation process.

• A hazard evaluation is performed before assessing the technical feasibility of a new process

. Chemical handling/storage criteria, critical process conditions, quality measurements, thermal hazards, and post

- campaign cleanup are considered in the introduction of any new process/product.Reactives Hazard Investigation 10
- 17
- 02, page 118

• Once a new process is identified as feasible, it goes through a process hazard analysis (usually HAZOP) to evaluate issues such as reactive chemistry.

• Hazard evaluations are conducted in a team environment that typically includes a process engineer, EHS staff, a chemist, maintenance, a production operator, and the c ustomer.

• Design reviews are conducted to refine requirements. Hazards are introduced to plant operators following laboratory work, EHS review, capital requirements review, and process hazard analysis. Reactivity is addressed during process hazard analysi s and the initial review.

• A HAZOP is performed on all new chemicals following process review, preliminary equipment review, and development of preliminary standard operating procedures (SOP). “What

- if” and checklists are typically used to review a process without process design and chemistry changes.

• Process chemistry changes are evaluated for quality and EHS impacts.

• MOC and SOPs are vehicles for approving and communicating change.



### C.2.3.4 Risk Reduction/Controls

• Process hazard analysis leads to risk re duction/control recommendations.

• Risk reduction/control is primarily accomplished through design measures, SOPs, and training.Reactives Hazard Investigation 10
- 17
- 02, page 119



### C.2.3.5 Communication and Training

• Once a new chemical is introduced into the plant, employees receive on

- the

- job training on the new production process, which covers safe operating limits, process controls, emergency situations, etc.

• Operators have levels of expertise. The most experienced operators (level 3) generally perform the majority of the process

- related functions. Entr y - level operators are not assigned this work, and level 2 operators perform these functions with supervision.



### C.2.4 Company D (Large Pharmaceutical Manufacturer) C.2.4.1 Program Philosophy

• Reactive chemical hazard management is one element of an over all process safety program and is emphasized through thermal hazards evaluation.

• The program is driven by previous incidents, concern for the community, and business factors.


### C.2.4.2 Hazard Identification and Testing

• Hazard identification is built into t he design process.

• Testing is conducted regardless of supplier information.

• The program includes a preliminary screening test, team

- based screening, reactive evaluation, and process hazard analysis.

• The reactive hazard evaluation protocol is nonprescripti ve; the type and quantity of testing isReactives Hazard Investigation 10
- 17
- 02, page 120

based on judgment.

• National Fire Protection Association (NFPA) ratings are used for original screening; no chemicals with NFPA ratings of 3 or 4 are used at the site.

• The company has a full range of reactive chemical test equipment onsite.



### C.2.4.3 Hazard Evaluation

• A complete evaluation is conducted during process development, including testing and system evaluation of process aberrations.

• A multidisciplinary team approach is used during all phases of evaluation.

• A binary interaction matrix is developed for all materials in the process, including air and
rust.

• The PHA method is case dependent, focused on procedure, and required for every pilot

- plant

run.

• Process hazard analysis considers equipment failure, human fact ors

– including errors of omission and commission, and previous incidents.



### C.2.4.4 Risk Reduction and Controls

• Risk is identified at various stages in the process.

• Special setups are used to control risk.

• The process hazard analysis identifies operator tra ining needs.Reactives Hazard Investigation 10
- 17
- 02, page 121

• Risk assessment is qualitative.


### C.2.4.5 Communications and Training

• Incident data are kept in a local database and shared both site

- and company

- wide.

• There is no formal pharmaceutical industry trade group that dicusses safety issues.



### C.2. 5 Company E (Large Chemical Manufacturer) C.2.5.1 Program Philosophy

• Reactive chemicals hazard management is part of the overall process safety program, which is applied regardless of regulatory coverage.

• Codes of practice developed at the corporate l evel promote standardization throughout the
company.


### C.2.5.2 Hazard Identification and Testing

• Reactive chemical testing is done at the corporate level.

• The company maintains a list of chemicals that are considered to be highly hazardous based on such ch

aracteristics as flash point (less than 100°F), self reactivity, water reactivity, boiling point, and toxicity.



### C.2.5.3 Hazard Evaluation

• Plants are periodically audited against rigid corporate guidelines for safe operation.

• Multidisciplinary teams con duct process hazard analyses.Reactives Hazard Investigation 10
- 17
- 02, page 122

• Exceptions to corporate guidelines are made by committee.

• Process hazard analyses are conducted in accordance with formal procedure, with piping and instrumentation diagrams for reference.



### C.2.5.4 Risk Reduction and Controls

• The company generates a standard MSDS for all raw materials and products.

• Corporate guidelines dictate procedures for safe limits of operation and response to a runaway reaction.

• Color

- coded buckets and storage locations protect against inadvertent mixing of incompatible chemicals.

• An interaction matrix is available on the intranet.


### C.2.5.5 Communications and Training

• The company offers comprehensive training on plant safety policies.Reactives Hazard Investigation 10
- 17
- 02, page 123



## APPENDIX D: Resources

D.1 Guidelines There are extensive writings on reactive hazard management. The term “guidelines” is used herein to refer to good practices that are nonmandatory and are developed through industry consortia, committees, professional societies, and other bodies.
CSB analysis included guidelines th at focus primarily on the process safety of reactive chemicals; other good practices that might include some elements of reactive process safety were not included.



### D.1.1 CCPS Guidelines Series In 1985, the American Institute of Chemical Engineers (AICh E) established the Center for Chemical Process Safety (CCPS) to aid in the prevention or mitigation of catastrophic chemical accidents. CCPS publishes a series of Guidelines books and bulletins on good management and engineering practices, including the f

ollowing on reactive hazard management:

• Guidelines for Chemical Reactivity Evaluation and Application to Process Design, 1995
This publication describes the principles for evaluating chemical reactivity as an element of chemical process design. It outli nes methods for identifying reaction hazards and establishing safe operating conditions. Special emphasis is placed on state

- of

- the

- art theory and testing methods, as well as inherent safety principles. The intended audience is those involved in R&D, pil

ot

- plant, process design, and (to a lesser degree) commercial plant operations. The guidelines focus on technical issues; they are not intended to be a manager’s guide to reactive hazard management.Reactives Hazard Investigation 10
- 17
- 02, page 124

• Guidelines for Safe Storage and Handling of Reactive Ma terials, 1995
This book summarizes current industry practices for design and operation of reactive chemical storage and handling systems. Special emphasis is placed on the engineering design of storage and handling systems. The intended audience is prima rily process engineers or others with technical responsibility

– not managers. The guidelines do not cover chemical reactions, mixing, or blending.

• Safety Alert, Reactive Material Hazards, 2001

This 10

- page bulletin offers an introduction to reactive ma terial hazards. It is organized around four key questions: Do you handle reactive materials? Can you have reactive interaction? What data do you need to control these hazards? What safeguards do you need to control these hazards?



### D.1.2 Other Guidan ce Other international publications offer guidance on the topic of reactive hazard management, such as:

• Chemical Reaction Hazards, A Guide to Safety, 1997
The purpose of this guidebook, written by Barton and Rogers for the Institution of Chemical Engineers (IChemE), is to provide a basis for good practice in assessing reactive hazards. It is written for those responsible for design and operation of chemical plants. It addresses hazards from uncontrolled exothermic activity in batch and semibatch chemical reaction systems as well as associated process equipment.Reactives Hazard Investigation 10
- 17
- 02, page 125

• Designing and Operating Safe Chemical Reaction Processes, 2000
The intent of this book, published by the Health and Safety Executive (HSE) of the United Kingdom, is to guide programs for small

- and medium

- sized chemical manufacturing companies using batch and semibatch manufacturing processes. Its intended audience is those directly responsible for the development, design, and operation of chemical plants and processes, particularly process chemist s and process engineers. The objectives of the HSE guidance are to:

- Increase awareness of potential reactive hazards.

- Assist in the assessment of risks.

- Provide a systematic approach for the design, operation, and control of chemical reactions in batch a nd semibatch processes.

- Advise on safe management procedures.

- Advise on maintenance, training, and information needs to prevent and control reactive hazards.



## D.2 Future Guidance At least two efforts are currently underway to develop additional guidance in the area of reactive hazard management:

• CCPS project on the management of reactive chemical hazards
As the result of a number of recent incidents caused by inappropriate handling of reactive chemicals, CCPS initiated a project in 2001 to develop additio nal management guidelines for reactive hazards. A CCPS technical steering committee documented the urgent need forReactives Hazard Investigation 10
- 17
- 02, page 126

comprehensive “best practice” guidelines.
The audience is expected to be process safety professionals, engineers, chemists, and other techni cal personnel who generate data and design processes that involve reactive chemicals. Manufacturing personnel who operate such facilities are also expected to benefit through improved understanding of risks.

• Hazard Assessment of Highly Reactive Systems T hematic Network (HarsNet).
HarsNet is a thematic network project sponsored by the European Commission’s Industrial and Materials Technologies Program. It is coordinated through the Instituto Químico de Sarrià, with participation by government organization s, universities, major companies (e.g., Dow, BASF, and CIBA), and private testing services.
The objectives of HarsNet are to:

- Analyze existing methodologies for thermal hazard assessment and prevention.

- Prepare guidelines for thermal hazard assessment a nd prevention.

- Disseminate knowledge and methodologies to small

- and medium

- sized enterprises.

- Provide technical support to small

- and medium

- sized enterprises.
HarsNet maintains that reactive chemical testing and analysis is too complex for most small

an d medium

- sized companies because of the wide spectrum of processes and equipment involved. The project seeks to provide an industry guide for estimating the thermal hazard of a chemical synthesis without sophisticated testing and analysis.Reactives Hazard Investigation 10
- 17
- 02, page 127



## D.3 ASTM Codes and Standards The American Society for Testing and Materials (ASTM) is a not

- for

- profit organization that provides a forum for the development and publication of voluntary consensus standards for materials, products, systems, and services. 67 One ASTM com mittee (E27) develops standardized physical and chemical test methods on the hazard potential of chemicals, including but not limited to reactive hazards. The committee has developed standard analytical methods for calorimetry studies in addition to a sta ndard guide for determining binary chemical compatibility (ASTM, 2000).
ASTM also distributes the computer program CHETAH (Chemical Thermodynamic and Energy Release Evaluation), a tool for predicting both thermodynamic properties and certain reactive haz ards associated with a pure chemical, a mixture of chemicals, or a chemical reaction.



## D.4 Select Resources on Reactive Hazards A variety of tools and resources are available to aid in the recognition of reactive hazards. Table D

- 1 provides a list and brie f description of selected literature resources and computerized tools.

67 ASTM standards are developed voluntarily and used voluntarily. They become leg ally binding only when a government body makes them so or when they are cited in a contractReactives Hazard Investigation 10
- 17
- 02, page 128

Table D - 1
Select Resources on Reactive Hazards Title Contents Source Bretherick’s Handbook of Reactive Chemicals Summaries of reactivity, incompatibility, and other dangerous propert ies of individual substances either alone or in combination; case histories Butterworth

- Heinemann

Sax’s Dangerous Properties of Industrial Materials Summaries of reactivity, incompatibility, and other dangerous properties; applicable standards and recomm

endations; hazard rating VanNostrand Reinhold (Lewis)

Rapid Guide to Chemical Incompatibilities Summaries of known effects of dangerously reactive substances Wiley and Sons (Pohanish and Greene) The Chemical Reactivity Worksheet Database of reactivity information for more than 4,000 common chemicals; includes information on special hazards of each chemical and whether a chemical reacts with air, water, or other materials; predicts the reactivity between two chemicals National Oceanic and Atmospheric Ad ministration (NOAA)

CASREACT Database of abstracts related to reaction chemistry, including hazard/safety information American Chemical Society (Chemical Abstract Service) Chemical Hazards Response Information System (CHRIS) Database on chemical and ph ysical properties; guides to compatibility of chemicals U.S. Coast Guard (USCG)

Material Safety Data Sheets (MSDS) Data on chemical and physical properties, and other dangerous properties Chemical manufacturer

Guidelines for Chemical Reactivity Evaluatio n and Application to Process Design Fundamentals for identification and evaluation of reactive hazards CCPS
Guidelines for Safe Storage and Handling of Reactive Materials Design of storage and handling systems for reactive chemicals CCPS
Reactive Materia l Hazards, What You Need to Know Introduction to reactive issues CCPS Safety and Runaway Reactions Articles on reactive hazards Institute for Systems Informatics and Safety Chemical Reaction Hazards, A Guide to Safety Fundamentals of reactive hazards IC hemE (Barton and Rogers) Designing and Operating Safe Chemical Reaction Processes Safe design and operation of plants and processes for chemical reactions HSE
Safety of Reactive Chemicals and Evaluation of reactive hazards and Elsevier (Yoshida, Wada, andReactives Hazard Investigation 10
- 17
- 02, page 129

Title Contents Source Pyrotechnics case histories Foster) CRC Handbook of Chemistry and Physics Data on chemical properties, especially thermochemistry, kinetics, and molecular structure CRC Press (Lide)

Encyclopedia of Chemical Technology Articles on chemical manufacturi ng of either single substances or groups of substances. Wiley and Sons ( Kirk

- Othmer)
Chemistry of Hazardous Materials Fundamentals of hazardous properties Brady, Prentice

- Hall (Meyer) Ashford’s Dictionary of Industrial Chemicals Hazardous properties of particular chemicals Wavelength Publications A Comprehensive Guide to the Hazardous Properties of Chemical Substances Correlates the chemical structure of compounds to their hazardous properties Wiley and Sons (Patnaik)

Sittig’s Handbook of Toxic and H azardous Chemicals and Carcinogens Data on chemical properties and chemical incompatibility William Andrew Publishing

Hazardous Chemicals Desk Reference Chemical property data on safe handling and storage, applicable standards and recommendations, hazard rating Wiley and Sons (Lewis)

NFPA 491M Manual of Hazardous Chemical Reactions Data on hazardous chemical reactions National Fire Protection Association (NFPA) NFPA 43 B Storage of Organic Peroxide Formulations Hazards of peroxides NFPA
NFPA 49 Hazardo us Chemicals Data Chemical hazard information, including reactivity data NFPA NFPA 325 Fire Hazard Properties of Flammable Liquids, Gases, and Volatile Solids Chemical hazard information, including reactivity ratings NFPA

NFPA 430 Storage of Liquid and S olid Oxidizers Hazards of oxidizers NFPAReactives Hazard Investigation 10
- 17
- 02, page 130



## Appendix E: Hazard Investigation Data Sources

Title Source 

### CSB Action
Process Safety Incident Database Center for Chemical Process Safety (CCPS)/American Institute of Chemical Engineers (AIChE) Proprietary

- un available

National Response Center (NRC) Data U.S. Coast Guard (USCG) Retrieved information
Integrated Management Information System (IMIS) Occupational Safety and Health Administration (OSHA) Retrieved information

The Accident Database Institution of Chemical Engineers (IChemE) Retrieved information
Accidental Release Information Program (ARIP) U.S. Environmental Protection Agency (EPA) Retrieved information
RMP*Info (Five

- Year Accident History Data) EPA Retrieved information
Major Hazard Incid ent Data Service (MHIDAS) Health and Safety Executive, United Kingdom (HSE) Retrieved information
Chemical Incident Reports Center (CIRC) U.S. Chemical Safety and Hazard Investigation Board (CSB) Retrieved information

Fire Incident Data Organization Dat abase National Fire Protection Association (NFPA) Retrieved information
Reports of Chemical Safety Occurrences at U.S. Department of Energy (DOE) facilities DOE Retrieved information
Process Safety Code Measurement System American Chemistry Council (AC C) Reviewed only
National Fire Incident Reporting System U.S. Fire Administration Reviewed only
TNO Process Safety and Dangerous Goods (FACTS) Netherlands Organisation for Applied Scientific Research Reviewed only Major Accident Reporting System (MARS) European Communities Major Accident Hazard Bureau (MAHB) Reviewed only

Mary Kay O'Connor Process Safety Center Database Texas A&M University Reviewed only
Hazardous Substances Emergency Events Surveillance (HSEES) MAHB Reviewed onlyReactives Hazard Investigation 10
- 17
- 02, page 131



### Title Source 

### CSB Action
The Community Docu mentation Centre on Industrial Risk (CDCIR) MAHB Reviewed only
Awareness and Preparedness for Emergencies at Local Level (APELL) United Nations Environmental Programme (UNEP) Reviewed only

Acute Hazardous Events Database EPA Reviewed only

Census of Fa tal Occupational Injuries (CFOI) U.S. Bureau of Labor Statistics Reviewed only
Process Safety Database American Petroleum Institute (API) Reviewed only
The European Health and Safety Database (HASTE) European Foundation for the Improvement of Living and Working Conditions Reviewed only

Various Chlorine Related Incident Reports Chlorine Institute Retrieved information
Hazardous Materials Incident Reports National Transportation Safety Board (NTSB) Retrieved information
Fire Incident Reports NFPA Retrie ved information
Annual Loss Prevention Symposium (CD ROM) CCPS Retrieved information
Bretherick's Handbook of Reactive Chemical Hazards, 6th Ed. Butterworth

- Heinemann Retrieved information

Loss Prevention in the Process Industries F. P. Lees Retrieved i nformation Large Property Damage Losses in the Hydrocarbon Chemical Industries, A Thirty

- Year Review, 18th Ed. Marsh and McLennan Retrieved information
NAPP Technologies Chemical Accident Investigation Report EPA/OSHA Retrieved information

Prevention of

Reactive Chemical Explosions EPA Retrieved information
How to Prevent Runaway Reactions EPA Retrieved information
Tosco Avon Refinery Chemical Accident Investigation Report EPA Retrieved information
Surpass Chemical Company Chemical Accident Investigat ion Report EPA Retrieved information
Incidents in the Chemical Industry Due to Thermal Runaway Reactions Barton and Nolan Retrieved informationReactives Hazard Investigation 10
- 17
- 02, page 132



### Title Source 

### CSB Action

Lessons From Disaster T. Kletz Reviewed only
What Went Wrong? T. Kletz Reviewed only

Chemical Process Safet y, Lessons Learned from Case Histories R. Sanders Reviewed only
Explosions in the Process Industries IChemE Reviewed only
Chemical Reaction Hazards, A Guide to Safety, 2nd Ed. IChemE Reviewed only

NFPA 491 Guide for Hazardous Chemical Reactions NFPA Re viewed only
Proceedings of the 2nd International Symposium on Runaway Reactions, Pressure Relief Design, and Effluent Handling CCPS Reviewed only
Occurrence and Impact of Unwanted Chemical Reactions, Journal of Loss Prevention in the Process Industries 1 B. Rasmussen Reviewed only
Origins of Unwanted Reactions, Report M

- 2631 B. Rasmussen Reviewed only

Unwanted Chemical Reactions in the Chemical Process Industry B. Rasmussen Reviewed only
Intl. Conference and Workshop on Process Industry Incidents CCPS Reviewed only

Chemical Reaction Hazards and the Risk of Thermal Runaway HSE Reviewed only
Safety of Reactive Chemicals and Pyrotechnics, Industrial Safety Series, Volume 5 Yoshida, et al. Reviewed only
Safety and Runaway Reactions Mitchison and Snyeder Reviewed only
Safety of Chemical Batch Reactors and Storage Tanks Benuzzi and Zaldivar Reviewed onlyReactives Hazard Investigation 10
- 17
- 02, page 133



## APPENDIX F: Statistical Review of Occupational Fatalities
The U.S. Chemical Safety and Hazard Investigation Board (CSB) reviewed Bureau of Labor St atistics (BLS) data (1996

– 2000) on occupational fatalities to determine the significance of the reactive incident problem in the context of chemical process safety. 68 Table F

- 1 summarizes this information.

Table F - 1 Review of Occupational Fatalities

Yea r 1996 1997 1998 1999 2000 Total Total occupational fatalities 6,112 6,218 6,026 6,023 5,915 30,294 Fatalities in the chemical manufacturing industry (a) 40 62 91 78 41 272
Fatalities in the chemical manufacturing industry due to fire, explosion, and to xic substances (b) 16 23 46 46 16 147

Fatalities from reactive incidents in data collected by CSB 2 8 0 10 1 21

Fatalities from reactive incidents in the chemical manufacturing industry in data collected by CSB 0 3 0 7 (c) 1 11

(a) Chemical manufactu ring industry (SIC Division D Group 28). (b) Incidents that resulted in fires, explosions, and toxic releases are assumed to be process safety incidents. (c) In addition to occupational fatalities, there was also one public fatality from a reactive incide nt during 1999.

68 It is important to note that CSB analyzed BLS fatality data only within SIC Division D Group 28 (chemical manufacturing and allied products). Thus, the data pre sented in table F

- 1 is conservative in that it does not include fatalities that occurred to contractors or to personnel in other industries, such as petroleum refining, rubber products, paper products. Contractor fatalities are documented within BLS accor ding to the services the contract company provides. For example, in the ARCO incidents there were 17 fatalities, 5 ARCO employees (a chemical manufacturer under SIC Group 28) and 12 contractors (who had been working at the facility for several years). The fatalities to the ARCO employees were recorded under SIC Division D Group 28. However, the 12 contractor fatalities were not attributed to the chemical manufacturing industry rather they were grouped under the construction SIC. Thus, these 12 contractor fatalities would not have been included in our analysis of BLS data.Reactives Hazard Investigation 10
- 17
- 02, page 134

As described in Section 3.1, CSB data represent only a sampling of reactive incidents and should not be directly compared to BLS data, which offer a more complete accounting of occupational fatalities. Nonetheless, CSB data provide an i ndication that a significant number of fatalities from process safety incidents involve reactive hazards.Reactives Hazard Investigation 10
- 17
- 02, page 135



## APPENDIX G: Identifying Hazards Using Chemical Reactivity Testing
This appendix, which briefly illustrates how testing can be an integral part o f a reactive hazard management system, is provided to facilitate the discussion of alternative criteria for improving regulatory coverage in Section 8.0. It does not describe in detail testing methods, theory, or practical application. Further informatio n on these topics is provided in Grewer (1994), CCPS (1995a; 1995b), IChemE (Barton and Rogers, 1997), and HSE (2000). The Glossary (Appendix A) briefly defines each analytical test.
Screening is typically used to indicate when more detailed testing is ne cessary. The Center for Chemical Process Safety (CCPS, 1995b; p. 90) explains that the objective of thermal stability screening is to obtain data on the possibility of exothermic (heat generating) reaction for mixtures or self

- reaction for single substanc es. Screening calorimeters measure the energy produced by a reaction and the temperature at which energy is liberated. Differential screening calorimetry (DSC) is considered to be the primary screening test, though differential thermal analysis (DTA) is also used. Thermogravimetric analysis (TGA) can also be used to screen for stability at high temperature through precise weight loss
measurements.
Screening techniques are relatively cost

- effective and require only a small chemical sample; however, they do not measure gas evolution or maximum pressure rise. A material is generally considered to be thermally stable if the temperature at which energy from reaction is first observed is at least 100 degrees Celsius ( o C) above the maximum operating temperatu re of a process event under upset conditions (CCPS; 1995b; p. 93).
CCPS (1995b; p. 94) recommends more sensitive and sophisticated methods if screening calorimetryReactives Hazard Investigation 10
- 17
- 02, page 136

shows thermal instability at or near the temperature range of large

- scale storage or process ing. The next logical choice is adiabatic calorimetry, 69 which uses a larger sample and more advanced technology. This technique is more sensitive to detecting the onset temperature 70 for exothermic reactions, adiabatic temperature rise, and rate of reac tion; it also can measure pressure rise in a closed vessel, an important parameter in reaction scaleup. Compared to screening calorimetery, this sophisticated technique more accurately measures the overall energy of reaction, though the tests tend to be m ore costly and time intensive.
A common theme of industry guidelines is that every test result must be individually interpreted because of limitations and variations in conditions, and the complexity of the instrument. Factors such as sample size, conta iner material, and heating rate can greatly affect results. Therefore, personnel with appropriate training and experience should be consulted both before testing and for interpretation of results.
CCPS offers guidance on when to conduct testing for hazard identification. CCPS (1995a; p. 13) suggests that when designing processes for conducting chemical reactions, all materials should be subject to screening tests even if no reactivity concerns are identified in the literature search or by expert jud gment. In other guidance, CCPS (1995b; p. 85) states that that prior experience, theoretical evaluations, and expert opinion may be used to determine whether screening tests are necessary in designing storage and handling systems for reactive materials.

O ne of the factors that may be important in this determination is the possible rate of reaction. Theoretical evaluations can determine a large potential energy of reaction, but they do not determine how fast or slow that energy can be released. The rate o f reaction can be the critical factor in determining the severity of

69 In this context, the term “adiabatic” refers to calorimetry conducted under conditions that minimize heat losses to the surrounding environment to better simulate conditions in the pl ant, where bulk quantities of stored or processed material tend to minimize cooling effects. This class of calorimetry includes the accelerating rate calorimeter (ARC), from Arthur D. Little, Inc., and PHI

- TEC from Hazard Evaluation Laboratory Ltd. 70 Ons et temperature is the lowest temperature at which the test first observes an exothermic (heat liberating) reaction.Reactives Hazard Investigation 10
- 17
- 02, page 137

the reactive hazard (CCPS, 1995b; p. 86). When such uncertainties arise, an expert opinion may be needed to determine whether chemical testing is necessary.
Five of nine respondents t o the CSB survey frequently use both screening and more sophisticated approaches, including adiabatic calorimetry, to determine the thermal stability or compatibility of process materials. Seven of nine respondents use screening alone for chemical reactiv ity testing. The most often used testing objectives are:

• To determine the onset temperature of a runaway reaction using calorimetry.

• To determine thermal stability using screening tests.

• To determine gas evolution and maximum pressure rise.